JPH08269035A - Insecticidal (tetrahydro-3-furanyl) methyl derivative - Google Patents

Abstract

PURPOSE: To obtain a new compound having a high insecticidal potency and a wide insecticidal spectrum, and useful as an excellent insecticide. CONSTITUTION: A compound of formula I (R1 , R2 are each H or a 1-5C alkyl; R3 to R5 are each H, a 2-5C alkenyl, etc.; (n) is 2-5; R6 ,n is H or a 1-3C alkyl; X is CH or N; Y is nitro or cyano), e.g. N- (tetrahydro-3-furanyl)methyl}-N- methyl-N'- 2-nitro-1-(methylthio)ethenyl}ethylenediamine. To obtain this compound, a diamine of formula II is reacted with a compound of formula III (A is an alkylthio or a substituted imide) in acetonitrile or an alcohol. Furthermore, the compound of formula II is preferably obtained by reacting an (un)substituted tetrahydrofuran derivative such as (tetrahydro-3-furanyl)methylmesylate, etc., with a diaminoalkane derivative such as N-methylethylenediamine, etc.

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 Insecticidal compounds having a diaminoalkane group have already been disclosed (JP-A-63-10762). However, these patent publications specifically disclose only compounds having a nitrogen-containing unsaturated heterocycle, and do not disclose compounds 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 studies conducted by the present inventors to solve the above-mentioned problems, the (tetrahydro-3-furanyl) methyl derivative has a pyridylmethyl group or a thiazoylmethyl group as a molecular structure. They have found that they have excellent insecticidal activity, even though they do not have them inside, and completed the present invention. That is, the present invention provides the compound represented by the general formula (1)

[0005]

Embedded image [In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, and R ₃ , R ₄ and 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 or an optionally substituted carbon atom having 2 to 5 carbon atoms; Represents an alkynyl group, n represents an integer of 2 to 5, R _{6, n}
Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is CH
Alternatively, it represents a nitrogen atom, and Y represents a nitro group or a cyano group. Further, R ₃ and R ₄ may be taken together to form a ring. ] (Tetrahydro-3-furanyl) methyl derivative represented by the following and an insecticide containing the compound 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 a 1-butynyl group, a 2-butynyl group and a 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, tert-butylthio group, etc., chlorine atom, bromine atom, iodine atom A halogen atom of a fluorine atom, a hydroxyl group, an oxo group, a methanesulfonyl group, a trifluoromethanesulfonyl group, a sulfonyl group such as a tosyl group,
Silyl group such as trimethylsilyl group, phenyl group, 2-
Examples thereof include substituted or unsubstituted phenyl groups such as chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-methylphenyl group, 3-methylphenyl group and 4-methylphenyl group.

Regarding R ₃ , R ₄ and R ₅ , hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, propargyl group, benzyl group, 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.

R ₃ and R ₄ may be taken together to form a ring, and typical examples in this case are a methylene group, an ethylene group or a propylene group. n represents an integer of 2 to 5, preferably 2 to 4, and more preferably 2 or 3. R _{6, n} is, for example, a hydrogen atom or a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. X represents CH or a nitrogen atom, and Y represents a nitro group or a cyano group,
Preferably, X and Y together are a nitromethylene group or a nitroimino group.

Typical examples of the present invention will be given below, but the compounds of the present invention are not limited thereto. N-
{(Tetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N,
N'-dimethyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'-{2-nitro -1- (Methylthio) ethenyl} ethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N-{(4 -Methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} ethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N- { (5-Methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N -Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N'-{2-nitro- 1-
(Methylthio) ethenyl} ethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{2-nitro-1- (methylthio) ethenyl} ethylenediamine N- { (Tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N,
N'-Dimethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-Nitro-1- (methylthio) ethenyl} -1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-{2-nitro-1 -(Methylthio) ethenyl} -1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) Ethenyl} -1,3-diaminopropane

N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-
1- (methylthio) ethenyl} -1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) ethenyl}- 1,3-Diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) Ethenyl} -1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N,
N'-dimethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'- {2-Nitro-1- (methylthio) ethenyl} -1-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N ′-{2-nitro-1- (methylthio) Ethenyl} -1-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N′-dimethyl-N ′-{2-nitro-1-
(Methylthio) ethenyl} -1-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{2-nitro-1- (methylthio) ethenyl} -1-Methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methylethylenediamine N-{(5 -Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -1-methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-Methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N,
N'-Dimethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N -Methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-Nitro-1- (methylthio) ethenyl} -1-methyl-1,3-diaminopropane

N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-
Nitro-1- (methylthio) ethenyl} -1-methyl-
1,3-Diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methyl -1,3
-Diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methyl-1,3-diaminopropane N -{(5-Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1-methyl-1,3-diaminopropane N-{(5 -Methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -1-methyl-1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{2-nitro-1 -(Methylthio) ethenyl} -1-methyl-1,3
-Diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N,
N'-dimethyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'- {2-Nitro-1- (methylthio) ethenyl} -2-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) Ethenyl} -2-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -2-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} 2-Methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methylethylenediamine N-{(5 -Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -2-methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-Methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N,
N′-dimethyl-N ′-{2-nitro-1- (methylthio) ethenyl} -2-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methyl-1,3-diaminopropane

N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-
1- (methylthio) ethenyl} -2-methyl-1,3-
Diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methyl-1,3-diaminopropane N- {(4-Methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -2-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{2-nitro-1 -(Methylthio) ethenyl} -2-methyl-1,3
-Diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methyl-1,3-diaminopropane N -{(5-Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -2-methyl-1,3-diaminopropane N-{(5 -Methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -2-methyl-1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{2-nitro-1 -(Methylthio) ethenyl} -2-methyl-1,3
-Diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{2-nitro-1- (methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N,
N′-dimethyl-N ′-{2-nitro-1- (methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N -Methyl-N '-{2-nitro-1- (methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-Nitro-1- (methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N' -{2-Nitro-1-
(Methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{2-nitro-1 -(Methylthio) ethenyl} -3-methyl-1,3
-Diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -3-methyl-1,3-diaminopropane N -{(5-Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(5 -Methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{2-nitro-1-
(Methylthio) ethenyl} -3-methyl-1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{2-nitro-1 -(Methylthio) ethenyl} -3-methyl-1,3
-Diaminopropane

N-{(tetrahydro-3-furanyl) methyl} -N '-{2-nitro-1- (methylthio) ethenyl} piperazine N-{(4-methyltetrahydro-3-furanyl)} methyl-N' -{2-Nitro-1- (methylthio) ethenyl} piperazine N-{(5-methyltetrahydro-3-furanyl)} methyl-N '-{2-nitro-1- (methylthio) ethenyl} piperazine N-{( Tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{(nitroimino) (methylthio) methyl} ethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{(nitroimino) (methylthio) methyl} ethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N,
N'-dimethyl-N '-{(nitroimino) (methylthio) methyl} ethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} ethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'-{(nitroimino) (methylthio) Methyl} ethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} ethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl } -N, N'-Dimethyl-N '-{(nitroimino)
(Methylthio) methyl} ethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} ethylenediamine N-{(5- Methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{(nitroimino) (methylthio) methyl} ethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'- {(Nitroimino) (methylthio) methyl} ethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} ethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} ethylenediamine N-{(tetrahydro- 3-furanyl) methyl} -N-
Methyl-N '-{(nitroimino) (methylthio) methyl} -1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{(nitroimino) (methylthio) methyl} -1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N,
N'-dimethyl-N '-{(nitroimino) (methylthio) methyl} -1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'-{ (Nitroimino) (methylthio) methyl} -1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} -1, 3-Diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} -1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl}- 1,3-Diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{(nitroimino) (methylthio) methyl} -1,3-diaminopropane N-{(5 -Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} -1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl}- N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} -1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl}- 1,3-diaminopropane

N-{(tetrahydro-3-furanyl) methyl} -N-methyl-N '-{(nitroimino) (methylthio) methyl} -1-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl}- N-
Ethyl-N '-{(nitroimino) (methylthio) methyl} -1-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N,
N'-dimethyl-N '-{(nitroimino) (methylthio) methyl} -1-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -1-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'-{(nitroimino ) (Methylthio) methyl} -1-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N ′-{(nitroimino) (methylthio) methyl} -1-methylethylenediamine N- {(4-Methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} -1-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{(nitroimino) (methylthio) methyl} -1- Methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{(nitroimino) (methylthio) methyl} -1-methylethylenediamine N-{(5-methyltetrahydro-3- Furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} -1-methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(Nitroimino)
(Methylthio) methyl} -1-methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{(nitroimino) (methylthio) methyl} -1- Methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{(nitroimino) (methylthio) methyl} -1-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{(nitroimino) (methylthio) methyl} -1-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N,
N′-dimethyl-N ′-{(nitroimino) (methylthio) methyl} -1-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -1-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl- N '-{(nitroimino) (methylthio) methyl} -1-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-{(nitroimino) (Methylthio) methyl} -1-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} -1-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N′-methyl-N ′-{(nitroimino) (methylthio ) Methyl} -1-methyl-1,3-
Diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{(nitroimino) (methylthio) methyl} -1-methyl-1,3-diaminopropane N-{(5 -Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} -1-methyl-1,3-diaminopropane

N-{(5-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(nitroimino) (methylthio) methyl} -1-methyl-
1,3-Diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -1-methyl-1, 3-
Diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{(nitroimino) (methylthio) methyl} -2-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{(nitroimino) (methylthio) methyl} -2-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N,
N'-dimethyl-N '-{(nitroimino) (methylthio) methyl} -2-methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -2-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'-{(nitroimino ) (Methylthio) methyl} -2-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} -2-methylethylenediamine N- {(4-Methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} -2-methylethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -2- Methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{(nitroimino) (methylthio) methyl} -2-methylethylenediamine N-{(5-methyltetrahydro-3- Furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} -2-methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(Nitroimino)
(Methylthio) methyl} -2-methylethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -2- Methylethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{(nitroimino) (methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{(nitroimino) (methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N,
N'-dimethyl-N '-{(nitroimino) (methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl- N '-{(nitroimino) (methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-{(nitroimino) (Methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N′-dimethyl-N ′-{(nitroimino)
(Methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio ) Methyl} -2-methyl-1,3-
Diaminopropane

N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{(nitroimino) (methylthio) methyl} -2-methyl-1,3-diaminopropane N-{( 5-Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(5-methyltetrahydro-3- Furanyl) methyl} -N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} -2-methyl-1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio ) Methyl} -2-methyl-1,3-
Diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{(nitroimino) (methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{(nitroimino) (methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N,
N'-Dimethyl-N '-{(nitroimino) (methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N'-methyl-N '-{(nitroimino) (methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl- N '-{(nitroimino) (methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-{(nitroimino) (Methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio ) Methyl} -3-methyl-1,3-
Diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{(nitroimino) (methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(5 -Methyltetrahydro-3-furanyl) methyl} -N-ethyl-N '-{(nitroimino) (methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl ) Methyl} -N, N'-dimethyl-N '-{(nitroimino)
(Methylthio) methyl} -3-methyl-1,3-diaminopropane N-{(5-methyltetrahydro-3-furanyl) methyl} -N-ethyl-N'-methyl-N '-{(nitroimino) (methylthio ) Methyl} -3-methyl-1,3-
Diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N '
-{(Nitroimino) (methylthio) methyl} piperazine N-{(4-methyltetrahydro-3-furanyl)} methyl-N '-{(nitroimino) (methylthio) methyl} piperazine N-{(5-methyltetrahydro-3 -Furanyl)} methyl-N '-{(nitroimino) (methylthio) methyl} piperazine N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{(cyanoimino) (methylthio) methyl} ethylenediamine N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-N '-{(cyanoimino) (methylthio) methyl} -1,3-diaminopropane N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'-{(cyanoimino) (methylthio ) Methyl} ethylenediamine N-{(4-methyltetrahydro-3-furanyl) methyl} -N-methyl-N '-{(cyanoimino) (methylthio) methyl} -1,3-diaminopropane N-{(5-methyl Tetrahydro-3-furanyl) methyl} -N-methyl-N '-{(cyanoimino) (methylthio) methyl} ethylenediamine N-{(5-methyltetrahydro-3-furanyl) methyl} -N-methyl-N'-{ (Cyanoimino) (methylthio) methyl} -1,3-diaminopropane N-{(tetrahydro-3-furanyl) methyl} -N '
-{(Cyanoimino) (methylthio) methyl} piperazine N-{(4-methyltetrahydro-3-furanyl) methyl} -N '-{(cyanoimino) (methylthio) methyl} piperazine N-{(5-methyltetrahydro-3 -Furanyl) methyl} -N '-{(cyanoimino) (methylthio) methyl} piperazine

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) is represented by the following reaction formula (1)
Can be manufactured according to.

[0021]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _{6, n} , X,
Y and n have the same meanings as described above, and A represents an alkylthio group or a substituted imido group. That is, the compound represented by the general formula (1) can be easily prepared by reacting the diamine represented by the general formula (2) with the compound represented by the general formula (3) in acetonitrile or alcohol. Obtainable. Further, the diaminoalkane derivative represented by the general formula (2) can be produced according to the reaction formula represented by the following reaction formulas (2) and (Formula 4).

[0022]

[Chemical 4] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R _{6, n} and n have the same meanings as described above, and Z ₁ represents a halogen atom or a sulfonyloxy group.) That is, the general formula (2) The amine derivative represented by is obtained by reacting the substituted or unsubstituted tetrahydro-3-furan derivative represented by the general formula (4) with the diaminoalkane derivative represented by the general formula (5).

Further, in the production of the diaminoalkane derivative represented by the general formula (2), when the diaminoalkane derivative represented by the general formula (5) is asymmetric, an isomer is produced and purification becomes difficult. There are cases. In such a case, the following reaction formula (3) (formula 5) or reaction formula (4) (formula 6)
If you follow the instructions, you can synthesize efficiently.

[0024]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R _{6, n} (R _6,1 ), n
Represents the same meaning as described above, and Z ₂ represents a halogen atom or a sulfonyloxy group. )

[0025]

[Chemical 6] (In the formula, R ₁ , R ₂ , R ₃ , R _{6, n} (R _6,1 , R _6,2 ),
n has the same meaning as described above. ) That is, the substituted or unsubstituted tetrahydro-3-furanylmethylamine derivative represented by the general formula (6) and the halogenoacetic acid amide derivative (7) are reacted in the presence of a base to obtain an aminoacetic acid amide derivative ( It can be obtained by reducing 8) by a hydrogenation reaction using a metal hydride reagent such as lithium aluminum hydride or a metal catalyst. Alternatively, an aminopropionnitrile derivative (10) obtained by a Michael addition reaction between a substituted or unsubstituted tetrahydro-3-furanylmethylamine derivative represented by the general formula (6) and an acrylonitrile derivative (9).
Can be obtained in the same manner as above. Further, the substituted or unsubstituted tetrahydro-3-furanmethylamine derivative represented by the general formula (6) is represented by the following reaction formula (5) (chemical formula 7). It can be produced according to the reaction formula.

[0026]

[Chemical 7] (In the formula, R ₁ , R ₂ , R ₃ , and Z ₁ have the same meanings as described above.) That is, the substituted or unsubstituted tetrahydro-3-furan derivative represented by the general formula (4) and the general formula ( Obtained from the reaction with an alkylamine represented by 11). Also,
The substituted or unsubstituted tetrahydro-3-furanmethyl derivative represented by the general formula (4) has the following reaction formula (6).
It can be manufactured according to the reaction formula represented by (Chemical Formula 8).

[0027]

Embedded image (In the formula, R ₁ , R ₂ and Z ₁ have the same meanings as described above.) That is, a substituted or unsubstituted (tetrahydro-3-furan) methanol derivative represented by the general formula (12) is replaced with thionyl chloride, It can be obtained by reacting with a sulfonating agent such as p-toluenesulfonyl chloride and methanesulfonyl chloride in the presence of a halogenating agent such as phosphorus tribromide and a base such as triethylamine.

Further, the substituted or unsubstituted (tetrahydro-3-furan) methanol derivative represented by the general formula (12) and the alkyl-substituted compounds thereof can be easily and inexpensively prepared by a method known in the literature or a method similar thereto. Can be synthesized (Tetrahedron Letters, v
ol. 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),
Bull. Chem. Soc. Jpn. , Vo
l. 55, 1498-1503 (1982), Can.
J. Chem. , Vol. 39,923 (196
1)).

Further, some of the compounds represented by the general formula (3) are already known compounds, and are described, for example, in Chem.
Ber. , 100, 591-604, JP-A-4-
It is described in JP-A-74158 and JP-A-5-9173. And, as a concrete example thereof, 1,1-
Bis (methylthio) -2-nitroethylene, 1,1-bis (ethylthio) -2-nitroethylene, N-nitroimidodithiocarbonate dimethyl ester, N-nitroimidodithiocarbonate S-methyl-S-ethyl ester, N- Phthaloyl-S-methyl-N'-nitroisothiourea,
N-phthaloyl-S-ethyl-N′-nitroisothiourea and the like.

The compound 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.

Examples of such pests include armyworm, Tamanayaga, white-spotted armyworm, Spodoptera litura, Kaburagaga, Yotoga, Tamanaginuwaba, Nikamaiga, Kobunohimega, Heimadarameiga, rice beetle, cotton bollworm, potato, moth
Lepidoptera insect pests such as Nosima Madaraiga, Chanocha sukuensis, Kinmon Hosoga, Mikanhamogiga, Nashihime Shinkoi, Mameshino Shinga, Peach mosquito, Grape scabbard, Koga, Tobacco whitefly, Onitsutsuko whitefly, Mikantoge whitefly, Whitefly
Yukiyanagi aphid, apple aphid, green peach aphid, radish aphid, harbor aphid, bean aphid, orange aphid, wheat aphid, potato aphid, green aphid, green tea leafhopper, leafhopper leafhopper, blackhopper planthopper, blackhopper planthopper, blackhopper planthopper, leafhopper planthopper Taiwantsuno Tuna leafhopper, Yanoe scale scale, stag beetle scale, citrus scale scale,
Hemiptera pests such as the moss bug, the southern green stink bug, the leaf beetle, the beetle bug, the rice leaf weevil, the rice droopyworm, the dwarf worm, Diabrotica spp. Coleoptera pests such as, Pleurotus ostreatus, Pleurotus cornucopiae, Astragalus vulgaris, etc .; Culex pipiens, Culex pipiens, Aedes albopictus, Pleurotus spp. Thrips insects, such as thrips, oysters, thrips, thrips, rice thrips, and thrips thrips Orthoptera such as black cockroaches, American cockroaches, American cockroaches, German cockroaches, Cobainigo, and locust grasshoppers; Hymenoptera, such as turnips; , You can give a gage.

The fact that alkylenediamine derivatives having unsaturated heterocycles have insecticidal activity has already been reported in JP-A-63-
It is known from, for example, 10762. In this publication,
Although it is described that the optionally substituted 5- or 6-membered heterocyclic group containing at least one hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, Only compounds having a nitrogen unsaturated heterocycle are disclosed, and compounds having a saturated heterocycle are not disclosed. Moreover, the active compounds to be seen among these are limited to pyridine derivatives or thiazole derivatives. 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, and 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 control as a control 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 which is formulated to help the active ingredient reach the site to be treated and facilitate the storage, transportation and handling of the active ingredient compound. It means a natural inorganic or organic substance. Examples of suitable solid carriers include 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, vaseline, Organic substances such as lanolin, liquid paraffin, lard, vegetable oil,
Activated carbon etc. can be mentioned.

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

Further, these compounds represented by the formula (1) of the present invention can 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, Propaphos, Methylparathion, Temephos, Phoxime, Acephate, Isofenphos, Salithione, DEP, EPN, Ethione, Mecarbam, Pyridafenthione, Diazinon, Pirimiphos-methyl,
Etrimphos, isoxathion, quinalphos, chlorpyrifos-methyl, chlorpyrifos, phosalone, phosmet, methidathion, oxydebrophos, bamidthione,
Organophosphorus insecticides such as malathion, fentoate, dimethoate, formothion, thiomethone, ethyl thiomethone, folates, terbufos, profenophos, prothiophos, sulprophos, pyraclofos, monocrotophos, naredo, fostiazate, NAC, MTMC, MI
PC, BPMC, XMC, PHC, MPMC, ethiophene carb, bendiocarb, pirimicarb, carbosulfan, benfuracarb, mesomil, oxamyl,
Carbamate insecticides such as aldicarb, arylpropyl ether insecticides such as etofenprox and halfenprox, and silyl ether compounds such as silafluofene. Nicotine sulfate, polynactin complex,
Insecticidal natural products such as avermectin, milbemectin, BT agents, cartap, thiocyclam, bensultap, diflubenzuron, chlorfluazuron, teflubenzuron, triflumuron, flufenoxuron, flucycloxuron, hexaflumuron, fluazuron, imidacloprid, nitenpyram, acetamiprid. , Insecticides such as pymetrozine, fipronil, buprofezin, phenoxycarb, pyriproxyfen, methoprene, hydroprene, quinoprene, endosulfan, diafenthiuron, triazuron, tebufenozide, benzoepine, dicofol, chlorbendylate, phenisobromolate, tetradiphone , CPCBS, BPPS, quinomethionate, amitraz, benzomate, hexithiaxox, phen oxide Butanistan, cyhexatin, dienochlor, clofentezin, pyridaben, fenpyroximate, phenazaquin, tebufenpyrad, acaricide such as pyrimidinamine, other fungicides, fertilizers, soil conditioners, plant protection agents such as plant growth regulators, soil improving materials , A BT agent, a microbial production toxin, a natural or synthetic insect hormone disruptor, an attractant, a repellent, and a multipurpose composition having further excellent efficacy by mixing with other agricultural chemicals such as entomopathogenic microorganisms and small animals Can be created, 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 of the active ingredient is used.
~ 5000 ppm, preferably 0.01-1000 pp
It is desirable to use it at a concentration of m. 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-
Methyl-N ′-{2-nitro-1- (methylthio) ethenyl} ethylenediamine (Compound No. 8) (Tetrahydro-3-furanyl) methyl mesylate 1.
A mixture of 0 g, 5.0 g of N-methylethylenediamine, 1.53 g of anhydrous potassium carbonate, 0.50 g of sodium iodide and 10 ml of acetonitrile was boiled under reflux for 2 hours.
After filtration, the unreacted N-methylethylenediamine was distilled off by concentration under reduced pressure to obtain 0.86 g of an oily substance.

0.84 g of N-phthaloyl-N'-nitro-S-methylisothiourea was suspended in 10 ml of methylene chloride, and 0.50 g of the above oily substance was added dropwise at -10 ° C. After completion of dropping, the mixture was stirred at room temperature for 2 hours, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 0.16 of the desired product.
g was obtained.

Example 2 N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine (Compound No. 10) 1.08 g of N-phthaloyl-N'-nitro-S-methylisothiourea was suspended in 10 ml of methylene chloride, −
0.65 g of N-{(tetrahydro-3-furanyl) methyl} -N-ethylethylenediamine was added dropwise at 10 ° C. After completion of dropping, the mixture was stirred at room temperature for 2 hours, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 0.20 g of the desired product.
I got

Example 3 N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-N '-{2-nitro-1- (methylthio) ethenyl} -1,3-diaminopropane (Compound No. 3) N-{(tetrahydro-3-furanyl) methyl} -N-
Ethyl-1,3-diaminopropane 0.81 g, 1,1
-Bis (methylthio) -2-nitroethylene 0.78
A mixture of 10 g of acetonitrile and 10 ml of acetonitrile was boiled under reflux for 3.5 hours. The reaction solution was concentrated under reduced pressure, and the obtained oil was purified by column chromatography to give 0.34 g of the desired product as an oil.

Example 4 N-({tetrahydro-3-furanyl) methyl} -N-
Methyl-N ′-{(nitroimino) (methylthio) methyl} -1,3-diaminopropane (Compound No. 2) (Tetrahydro-3-furanyl) methyl mesylate 2.
5 g, N-methyl-1,3-diaminopropane 9.0
g, anhydrous potassium carbonate 3.84 g, sodium iodide 0.50 g, and a mixture of acetonitrile 50 ml were refluxed and boiled for 3 hours. After filtration, unreacted N-methyl-1,3-diaminopropane was distilled off by concentration under reduced pressure to obtain 2.22 g of an oily substance.

2.00 g of N-phthaloyl-N'-nitro-S-methylisothiourea was suspended in 10 ml of methylene chloride, and 1.00 g of the above oily substance was added dropwise at -10 ° C. After completion of dropping, the mixture was stirred at room temperature for 2 hours, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 0.50 of the desired product.
g was obtained.

Example 5 N-{(tetrahydro-3-furanyl} methyl} -N '
-{(Nitroimino) (methylthio) methyl} -1,4
-Diaminobutane (Compound No. 5) 0.30 g of N-phthaloyl-N'-nitro-S-methylisothiourea was suspended in 10 ml of methylene chloride,
1.0 g of N-{(tetrahydro-3-furanyl) methyl} -1,4-diaminobutane was added dropwise at 10 ° C. After completion of dropping, the mixture was stirred at room temperature for 2 hours, the reaction solution was discharged into 1N hydrochloric acid water, washed with hexane / ethyl acetate = 1/1, the aqueous layer was made basic with sodium hydroxide, and then with methylene chloride.
Extracted times. After drying over anhydrous sodium sulfate, concentration under reduced pressure,
The obtained oily substance was purified by silica gel column chromatography to obtain 0.76 g of the desired product.

Example 6 N-{(tetrahydro-3-furanyl) methyl} -N '
-{(Nitroimino) (methylthio) methyl} -1,5
-Diaminopentane (Compound No. 7) 0.64 g of N-phthaloyl-N'-nitro-S-methylisothiourea was suspended in 10 ml of methylene chloride,-
0.30 g of N-{(tetrahydro-3-furanyl) methyl} -1,5-diaminopentane was added dropwise at 10 ° C. After completion of dropping, the mixture was stirred at room temperature for 2 hours, discharged into 1N hydrochloric acid water, washed with hexane / ethyl acetate = 1/1, made the aqueous layer basic with sodium hydroxide, and then twice with methylene chloride. Extracted. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the obtained oily matter was purified by silica gel column chromatography to obtain 0.16 g of the desired product.

Example 7 N-{(tetrahydro-3-furanyl) methyl} -N '
-{2-nitro-1- (methylthio) ethenyl} -1,
5-diaminopentane (Compound No. 6) N-{(tetrahydro-3-furanyl) methyl} -1,
A mixture of 0.30 g of 5-diaminopentane, 0.40 g of 1,1-bis (methylthio) -2-nitroethylene and 10 ml of acetonitrile was boiled under reflux for 3.5 hours. The reaction solution was concentrated under reduced pressure, and the obtained oil was purified by column chromatography to obtain the desired product as an oil (0.13 g).

Example 8 N-{(tetrahydro-3-furanyl) methyl} -N '
-{2-nitro-1- (methylthio) ethenyl} -1,
4-diaminobutane (Compound No. 4) N-{(tetrahydro-3-furanyl) methyl} -1,
A mixture of 1.0 g of 4-diaminobutane, 0.95 g of 1,1-bis (methylthio) -2-nitroethylene and 10 ml of dimethylformamide (DMF) was boiled under reflux for 2 hours. The reaction solution was concentrated under reduced pressure, and the obtained oil was purified by column chromatography to obtain the desired product as an oil (0.45 g).

Reference Example 1 1- [N-{(tetrahydro-3-furanyl) methyl}
0.30 g of methylamino] -2-cyanoethane N-{(tetrahydro-3-furanyl) methyl} methylamine and 3 ml of acrylonitrile were stirred at 80 ° C for 2 hours. The reaction solution was subjected to silica gel column chromatography (silica gel, ethyl acetate: hexane = 1: 1).
Purification in 1) gave 0.24 g of colorless oil as the desired product.

Reference Example 2 N-{(tetrahydro-3-furanyl) methyl} -N-
Methyl-1,3-diaminopropane 0.35 g of lithium aluminum hydride was suspended in 10 ml of diethyl ether at 0 ° C., and 98% sulfuric acid of 0.
45 g was added carefully. After stirring at room temperature for 30 minutes, 1-
0.50 g of [N-{(tetrahydro-3-furanyl) methyl} methylamino] -2-cyanoethane was added, and the mixture was stirred at the same temperature for 3 hours. 0.40 g of water and 0.40 g of 2N sodium hydroxide solution were added, and the mixture was stirred for 30 minutes, filtered through a funnel with a glass filter, and the filtrate was concentrated under reduced pressure. 0.4 g of a target product was obtained as a crude oily substance.

Reference Example 3 N-{(tetrahydro-3-furanyl) methyl} -N-
Methylethylenediamine 0.35 g of lithium aluminum hydride was suspended in 10 ml of diethyl ether at 0 ° C. and stirred at room temperature for 30 minutes,
α- [N-{(tetrahydro-3-furanyl) methyl}
Methylamino] acetamide (0.50 g) was added, and the mixture was refluxed and boiled for 2 hours. 0.40 g of water and 0.40 g of 2N sodium hydroxide solution were added, and the mixture was stirred for 30 minutes, filtered through a funnel with a glass filter, and the filtrate was concentrated under reduced pressure. 0.4 g of a target product was obtained as a crude oily substance.

Reference Example 4 α- [N-{(tetrahydro-3-furanyl) methyl}
Methylamino] acetamide {N- (tetrahydro-3-furanyl) methyl} methylamine 1.00 g, α-chloroacetamide 0.80
g, anhydrous potassium carbonate 3.00 g, sodium iodide 0.20 g, and ethanol 20 ml were refluxed for 8 hours. The mixture was discharged into 20 ml of 2N sodium hydroxide, extracted with dichloromethane three times, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the desired product as a crude oily substance (1.03 g).

Reference Example 5 (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 6 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 = 8.1Hz), 3.65-3.88 (4H, m), 3.95 (1
H, dt, J = 5.9Hz, J = 8.1Hz), 7.71-7.80 (2H, m), 7.84-7.89 (2
H, m) IR (neat, cm ^-1 ): 1701,1399,1050,719

Reference Example 7 (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 8 (Tetrahydro-3-furanyl) methyl bromide Phosphorus tribromide 10 g, pyridine 0.8 g, ether 100
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 = 7.3Hz), 3.45-3.53 (1H, m), 3.60 (1
H, dd, J = 5.1Hz, J = 8.8Hz), 3.80 (1H, t, J = 7.3Hz), 3.89-3.95
(1H, m)

Reference Example 9 {(2-Methyltetrahydro-4-furanyl) methyl} amine hydrochloride (1) 13.0 g of (2-methyltetrahydro-4-furanyl) methanol and 12.5 g of triethylamine in 85 ml of tetrahydrofuran were cooled with ice. Under 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-{(2-methyltetrahydro-4-furanyl) methyl} phthalimide 22.1 g
Was obtained as colorless crystals. (2) N-{(2-methyltetrahydro-4-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 filtered off to obtain 5.70 g of {(2-methyltetrahydro-4-furanyl) methyl} amine hydrochloride 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 10 (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 a crude oily substance of diethyl- {2- (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.
A solution of diethyl (-ethoxycarbonyl) ethyl} malonate (17.4 g) in tetrahydrofuran (30 ml) was added dropwise over 20 minutes. The reaction solution was cooled under ice for 1 hour,
After stirring at room temperature for 5 hours, 10 ml of water was added dropwise over 20 minutes under ice cooling. The reaction solution was heated under reflux for 1 hour, filtered, and concentrated under reduced pressure to obtain 7.70 g of 2-hydroxymethyl-3-methyl-1,4-butanediol 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 11 (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 resulting oil was distilled under reduced pressure to obtain 14.8 g of diethyl 2- (2-oxopropyl) malonate 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 (5 mmHg) (2) 2- (2) under ice-cooling in a suspension solution of 5.00 g of lithium aluminum hydride in 100 ml of tetrahydrofuran under ice cooling.
A solution of 11.4 g of diethyl -oxopropyl) malonate in 30 ml of tetrahydrofuran was added dropwise over 20 minutes.
The reaction solution was stirred for 1 hour under ice cooling and for 4.5 hours at room temperature, and then 10 ml of water was added dropwise over 20 minutes under ice cooling. 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 12 3- (Methylaminomethyl) -4-ethyltetrahydrofuran (1) (3-ethyltetrahydro-4-furanyl) methanol 11.5 g, tosyl chloride 16.7 g, triethylamine 9.10 g, tetrahydrofuran 80 ml 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. Representative examples of the compound of the formula (1) produced according to the same method as in the above Examples and Reference Examples are shown in Table 1 (Tables 1 to 7) together with the compounds of the above Examples.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

[Table 6]

[0070]

[Table 7] In addition, according to the same method as in the above Examples and Reference Examples,
The following comparative compounds were prepared.

N- (Tetrahydro-2-furanyl) methyl-N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1,3-diaminopropane ¹ H NMR (CDCl ₃ , ppm): 1.41 -1.60 (1H, m), 1.78-2.08 (5H, m),
2.31 (3H, s), 2.43 (3H, s), 2.41-2.68 (4H, m), 3.52 (2H, br-
t), 3.73 (1H, q, J = 8.8), 3.86 (1H, q, J = 8.8), 4.01 (1H, quin
t, J = 6.6), 6.56 (1H, s), 10.79 (1H, br-s) IR (KBr, cm ^-1 ): 3152,2948,1563,1343,1234 Oil N- (4-pyridylmethyl)- N-methyl-N '-{2
-Nitro-1- (methylthio) ethenyl} ethylenediamine (compound described in JP-A-63-10762) ¹ HNMR (CDCl ₃ , ppm): 2.26 (3H, s), 2.43 (3H, s), 2.70 (2H, t, J
= 5.9), 3.49 (2H, q, J = 5.9) 3.58 (2H, s), 6.58 (1H, s), 7.35 (2H, d, J = 6.6), 8.57 (2H, d, J
= 6.6), 10.74 (1H, br-s) IR (KBr, cm ^-1 ): 3146,2811,1561,1415,1311,1220,1093 Next, the composition of the present invention will be specifically described with reference to formulation examples. To do.

Formulation Example 1 20 parts of the compound of the present invention, 10 parts of Solpol 355S (manufactured by Toho Kagaku Co., 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 part 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 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 2 (Table 8).

[0079]

[Table 8] Comparative compound 1: N-{(tetrahydro-2-furanyl)} methyl-N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1,3-diaminopropane Comparative compound 2: N- (4-Pyridylmethyl) -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} ethylenediamine (Compound described in JP-A-63-10762)

Test Example 2 Effect on Resistant Green Leafhopper The compound of the present invention is 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 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 3 (Table 9).

[0081]

[Table 9] Comparative compound 1: N-{(tetrahydro-2-furanyl) methyl} -N-methyl-N '-{2-nitro-1- (methylthio) ethenyl} -1,3-diaminopropane

[0082]

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.

Front page continuation (72) Inventor Atsuko Naoi 1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Shiro Shiraishi 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): [In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, and R ₃ , R ₄ and R ₅ are each independently Hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkenyl group having 2 to 5 carbon atoms or an optionally substituted carbon atom 2
5 represents an alkynyl group, n represents an integer of 2 to 5, R
_{6, n} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X represents a CH or a nitrogen atom, and Y represents a nitro group or a cyano group. Further, R ₃ and R ₄ may be taken together to form a ring. ] (Tetrahydro-3-furanyl) methyl derivative represented by this. 2. An insecticide containing the (tetrahydro-3-furanyl) methyl derivative represented by the general formula (1) according to claim 1 as an active ingredient.