JP2006321745A - Trifluoromethylsulfonylamidine derivative effective for controlling harmful organism - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new trifluoromethylsulfonylamidine derivative having excellent insecticidal and acaricidal activities. <P>SOLUTION: This trifluoromethylsulfonylamidine derivative is expressed by formula (1) [wherein, A is a 1-5C alkyl, a 3-5C cycloalkyl, OR<SP>2</SP>, NHR<SP>2</SP>or SR<SP>2</SP>; R<SP>1</SP>is H, a 1-3C alkyl, CH<SB>2</SB>OR<SP>2</SP>or C(=O)OR<SP>2</SP>; B is H, a halogen atom, methyl, trifluoromethyl or trifluoromethoxy; and R<SP>2</SP>is a 1-3C alkyl or a cycloalkyl]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a trifluoromethylsulfonylamidine derivative, a production method thereof, and use thereof.

Conventionally, pest control agents such as various insecticides have been studied (for example, Patent Documents 1 to 3). Patent Documents 1 to 3 disclose pest control agents using amidine compounds.
However, Patent Document 1 relates to an agricultural and horticultural fungicide and does not disclose a trifluoromethylsulfonyl group as a nitrogen substituent of a carbonylimino group (C = N).
Patent Document 2 discloses an amidine derivative used for an insecticide, but no trifluoromethylsulfonyl group is mentioned as a substituent of the amino nitrogen of the amidine bond.
Further, Patent Document 3 relates to a herbicide, and no trifluoromethylsulfonyl group is mentioned as a nitrogen substituent of the carbonylimino group.

On the other hand, pest control agents having a trifluoromethylsulfonamide group are disclosed (for example, Patent Documents 4 to 6).
However, Patent Document 4 and Patent Document 5 relate to insecticides and acaricides, but do not have amidine bonds and merely disclose sulfonamide compounds.
Patent Document 6 discloses a compound used for an indoor dust mite control agent, but does not have an amidine bond, but merely discloses a sulfonamide compound.
On the other hand, an amidine compound having a trifluoromethylsulfonyl group has been disclosed (for example, Non-Patent Document 1). However, the disclosed compound is a compound in which a trifluoromethylsulfonyl group is contained in both nitrogen atoms of the amidine bond, and a compound in which an alkyl group or a cycloalkyl group is contained in one nitrogen atom is not mentioned at all. Furthermore, there is no description about the use.

JP 56-22704 A JP-A-5-1034 JP-A-6-293738 JP 57-156407 A Japanese Patent Publication No. 63-24483 Japanese Patent Laid-Open No. 10-218857 J. Chem. Soc., Perkin Trans. 2, 2002, 1950-1955

  Accordingly, an object of the present invention is to provide a novel trifluoromethylsulfonylamidine derivative having excellent insecticidal and acaricidal activity.

（式中、
Ａは、Ｃ₁〜Ｃ₅アルキル基、Ｃ₃〜Ｃ₅シクロアルキル基、ＯＲ²基、ＮＨＲ²基又はＳＲ²基を表し、
Ｒ¹は、水素原子、Ｃ₁〜Ｃ₃アルキル基、ＣＨ₂ＯＲ²基又はＣ(＝Ｏ)ＯＲ²基を表し、
Ｂは、水素原子、ハロゲン原子、メチル基、トリフルオロメチル基又はトリフルオロメトキシ基を表し、
Ｒ²は、Ｃ₁〜Ｃ₃アルキル基又はシクロアルキル基を表し、
ｍは、１〜５の任意の整数を表し、
ただし、Ｂが複数存在する場合には、それらは同一でも、異なっていてもよい。）
で示されるトリフルオロメチルスルホニルアミジン誘導体。
２．次式(II)、

(式中、
Ａは、Ｃ₁〜Ｃ₅アルキル基又はＣ₃〜Ｃ₅シクロアルキル基を表す。)
で表される化合物と、
次式(III)、

(III)
(式中、
Ｂは、水素原子、ハロゲン原子、メチル基、トリフルオロメチル基又はトリフルオロメトキシ基を表し、
ｍは、１〜５の任意の整数を表し、
Ｒ¹は、水素原子、Ｃ¹〜Ｃ³アルキル基又はＣＨ²ＯＲ²基、Ｃ(＝Ｏ)ＯＲ²基を表し、
Ｒ²は、Ｃ１〜Ｃ３アルキル基又はシクロアルキル基を表し、
ただし、Ｂが複数存在する場合には、それらは同一でも、異なっていてもよい。)
で表される化合物と、
を塩基の存在下で反応させること上記１項に記載のトリフルオロメチルスルホニルアミジン誘導体の製造方法。





３．次式(IV)、

(式中、
Ａは、Ｃ₁〜Ｃ₅アルキル基、Ｃ₃〜Ｃ₅シクロアルキル基を表し、
Ｂは、水素原子、ハロゲン原子、メチル基、トリフルオロメチル基又はトリフルオロメトキシ基を表し、
ｍは、１〜５の任意の整数を表し、
ただし、Ｂが複数存在する場合には、それらは同一でも、異なっていてもよい。)
で表される化合物と、
次式(Ｖ)、

で表される化合物と、
を塩基の存在下で反応させることを特徴とする、上記１項に記載のトリフルオロメチルスルホニルアミジン誘導体の製造方法。
４．次式（VI）、

(式中、
Ｒ¹は、水素原子、Ｃ₁〜Ｃ₃アルキル基、ＣＨ₂ＯＲ²基、Ｃ(＝Ｏ)ＯＲ²基を表し、
Ｂは、水素原子、ハロゲン原子、メチル基、トリフルオロメチル基又はトリフルオロメトキシ基を表し、
ｍは、１〜５の任意の整数を表し、
ただし、Ｂが複数存在する場合には、それらは同一でも、異なっていてもよい。)
で表される化合物と、
次式（VII）、

（式中、
Ｒ^２は、Ｃ_１〜Ｃ_３アルキル基又はシクロアルキル基を表し、
Ｙは、ＮＨ₂基、ＳＨ基又はＯＨ基を表す。）
で表される化合物と、
を塩基の存在下で反応させることを特徴とする、





次式（VIII）、

（式中、
Ｒ²は、Ｃ₁〜Ｃ₃アルキル基又はシクロアルキル基を表し、
Ｚは、ＮＨ基、硫黄原子又は酸素原子を表す。）
で表されるトリフルオロメチルスルホニルアミジン誘導体の製造方法。
５．次式（IX）、

（式中、
Ａは、Ｃ₁〜Ｃ₅アルキル基、Ｃ₃〜Ｃ₅シクロアルキル基、ＯＲ²基、ＮＨＲ²基又はＳＲ²基を表し、
Ｂは、水素原子、ハロゲン原子、メチル基、トリフルオロメチル基又はトリフルオロメトキシ基を表し、
Ｒ²は、Ｃ₁〜Ｃ₃アルキル基又はシクロアルキル基を表し、
ｍは、１〜５の任意の整数を表し、
ただし、Ｂが複数存在する場合には、それらは同一でも、異なっていてもよい。）
で表される化合物と、
次式（X）、

(式中、
Ｒ³は、Ｃ₁〜Ｃ₃アルキル基、ＣＨ₂ＯＲ²基、Ｃ(＝Ｏ)ＯＲ²基を表し、
Ｘは、脱離基を表す。）
で表される化合物と、
を塩基の存在下で反応させることを特徴とする、
次式（XＩ）、

（式中、
Ａは、Ｃ₁〜Ｃ₅アルキル基、Ｃ₃〜Ｃ₅シクロアルキル基、ＯＲ²基、ＮＨＲ²基又はＳＲ²基を表し、
Ｒ³は、Ｃ₁〜Ｃ₃アルキル基、ＣＨ₂ＯＲ²基又はＣ(＝Ｏ)ＯＲ²基を表し、
Ｂは、水素原子、ハロゲン原子、メチル基、トリフルオロメチル基又はトリフルオロメトキシ基を表し、
Ｒ²は、Ｃ₁〜Ｃ₃アルキル基又はシクロアルキル基を表し、
ｍは、１〜５の任意の整数を表し、
ただし、Ｂが複数存在する場合には、それらは同一でも、異なっていてもよい。）
で示されるトリフルオロメチルスルホニルアミジン誘導体の製造方法。 As a result of investigating and studying conventionally known compounds, the present inventors have found that a compound having a specific trifluoromethylsulfonyl group as a nitrogen substituent of the carbonylimino group of an amidine bond has excellent insecticidal and acaricidal activity. The headline, the present invention has been reached.
That is, the present invention relates to the following inventions.
1. The following formula (I),

(Where
A represents a C ₁ -C ₅ alkyl group, a C ₃ -C ₅ cycloalkyl group, an OR ² group, an NHR ² group or an SR ² group,
R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group or a C (═O) OR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
A trifluoromethylsulfonylamidine derivative represented by:
2. Formula (II)

(Where
A represents a C ₁ -C ₅ alkyl or C ₃ -C ₅ cycloalkyl group. )
A compound represented by
Formula (III)

(III)
(Where
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
m represents an arbitrary integer of 1 to 5,
R ¹ represents a hydrogen atom, a C ¹ -C ³ alkyl group or a CH ² OR ² group, a C (═O) OR ² group,
R ² represents a C1-C3 alkyl group or a cycloalkyl group,
However, when a plurality of B are present, they may be the same or different. )
A compound represented by
The method for producing a trifluoromethylsulfonylamidine derivative according to the above 1, wherein the reaction is carried out in the presence of a base.





3. Formula (IV)

(Where
A represents C ₁ -C ₅ alkyl group, a C ₃ -C ₅ cycloalkyl group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
A compound represented by
The following formula (V),

A compound represented by
The method for producing a trifluoromethylsulfonylamidine derivative according to the above 1, characterized in that is reacted in the presence of a base.
4). Formula (VI)

(Where
R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group, a C (═O) OR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
A compound represented by
Formula (VII)

(Where
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
Y represents an NH ₂ group, an SH group or an OH group. )
A compound represented by
In the presence of a base,





Formula (VIII),

(Where
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
Z represents an NH group, a sulfur atom or an oxygen atom. )
The manufacturing method of the trifluoromethylsulfonylamidine derivative represented by these.
5. Formula (IX),

(Where
A represents a C ₁ -C ₅ alkyl group, a C ₃ -C ₅ cycloalkyl group, an OR ² group, an NHR ² group or an SR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
A compound represented by
The following formula (X),

(Where
R ³ represents a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group, a C (═O) OR ² group,
X represents a leaving group. )
A compound represented by
In the presence of a base,
The following formula (XI),

(Where
A represents a C ₁ -C ₅ alkyl group, a C ₃ -C ₅ cycloalkyl group, an OR ² group, an NHR ² group or an SR ² group,
R ³ represents a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group or a C (═O) OR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
The manufacturing method of the trifluoromethylsulfonylamidine derivative shown by these.

  The trifluoromethylsulfonylamidine derivative of the present invention has an excellent insecticidal or acaricidal effect.

Hereinafter, the present invention will be described in detail.
The amidine derivative of the present invention is a compound having a structure represented by the above formula (I).
In the above formula, A represents a C ₁ -C ₅ alkyl group, a C ₃ -C ₅ cycloalkyl group, an OR ² group, an NHR ² group or an SR ² group,
R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group, a C (═O) OR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group.

Here, the C ₁ -C ₅ alkyl group as A may be linear or branched. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 1- Examples include methylpropyl group, 1,1-dimethylethyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, and 1-ethylpropyl group, preferably methyl group, ethyl group, isopropyl Preferred examples include C ₁ -C ₃ alkyl groups such as groups.
Examples of the C _{3 to} C ₅ cycloalkyl group as A include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group, and a cyclopropyl group and a cyclopentyl group are preferable.

Preferred examples of the halogen atom as B include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The C ₁ -C ₃ alkyl group as R ¹ may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
Range of C ₁ -C ₃ alkyl group as R ² are the same as those of R ^1. In addition to the case of R ¹ , the cycloalkyl group as R ² includes a cycloalkyl group having 6 or more carbon atoms.

Next, a method for producing the amidine derivative of the present invention will be described.
The amidine derivative of the present invention can be produced, for example, according to the following production methods 1 to 4. Unless otherwise specified, the symbols in the formula have the above meanings.
Manufacturing method 1
Compound (I) of the present invention is obtained by reacting compound (II) with compound (III) in the presence of a base.

The reaction is usually performed in an inert solvent in the presence of a base.
The inert solvent used in the reaction is not particularly limited as long as it does not inhibit the reaction, and various solvents can be appropriately used. Examples of such an inert solvent include acid amides such as N-methylpyrrolidone and N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, organic sulfurs such as dimethyl sulfoxide, toluene, and the like. And aromatic hydrocarbons such as benzene, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, and mixtures thereof.
Preferable examples of the base used in the reaction include organic bases such as pyridine, 4-dimethylaminopyridine and triethylamine, and inorganic bases such as sodium hydride and potassium carbonate.

The amount of the base is usually 1 to 10 mol, preferably 1 to 1.5 mol, per 1 mol of compound (III).
The amount of compound (II) to be subjected to the reaction is usually 1 to 10 mol, preferably 1 to 1.5 mol, per 1 mol of compound (III).
The reaction temperature is usually in the range of −20 ° C. to the boiling point of the reaction solvent, and preferably in the range of 0 ° C. to room temperature.
The reaction time is usually 1 to 72 hours, preferably 1 to 24 hours.
After completion of the reaction, the target compound of the present invention can be isolated by performing post-treatment operations such as filtering the salt as it is, or pouring the reaction mixture into water, extracting with an organic solvent and concentrating. .
If necessary, it can be purified by chromatography, recrystallization or the like.

Production method 2 (in formula (I), when substituent R ¹ is a hydrogen atom)
Compound (VIII) of the present invention is obtained by reacting compound (IV) with compound (V) in the presence of a base.

This reaction is usually performed in an inert solvent in the presence of a base. The inert solvent used in the reaction may be anything as long as it does not inhibit the reaction. For example, acid amides such as N-methylpyrrolidone and N, N-dimethylformamide, ethers such as tetrahydrofuran and diethyl ether, etc. Preferred examples include organic sulfurs such as dimethyl sulfoxide, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, and mixtures thereof.
Examples of the base used for the reaction include pyridine, organic bases such as 4-dimethylaminopyridine and triethylamine, inorganic bases such as sodium hydride and potassium carbonate, and alkali metal alkoxides such as potassium tert-butoxide. Can be mentioned.
The amount of the base used in the reaction is usually 2 to 10 mol, preferably 2 to 3 mol, per 1 mol of compound (V).
The amount of compound (IV) to be subjected to the reaction is usually 1 to 10 mol, preferably 1 to 1.5 mol, per 1 mol of compound (V).
The reaction temperature is usually in the range of −20 ° C. to the boiling point of the reaction solvent, and preferably in the range of 0 ° C. to room temperature.
The reaction time is, for example, 1 to 72 hours, preferably 1 to 24 hours.
After completion of the reaction, the target compound of the present invention can be isolated by performing post-treatment operations such as filtering the salt as it is, or pouring the reaction mixture into water, extracting with an organic solvent and concentrating. .
If necessary, it can be purified by chromatography, recrystallization or the like.

Production method 3
Compound (VIII) of the present invention is obtained by reacting compound (VI) with compound (VII) in the presence of a base.

In the formula, Y represents an NH ₂ group, an SH group or an OH group.
This reaction is usually performed in an inert solvent in the presence of a base. The inert solvent used in the reaction may be anything as long as it does not inhibit the reaction. For example, acid amides such as N-methylpyrrolidone and N, N-dimethylformamide, ethers such as tetrahydrofuran and diethyl ether, etc. And organic sulfurs such as dimethyl sulfoxide, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, and mixtures thereof.
Examples of the base used for the reaction include pyridine, organic bases such as 4-dimethylaminopyridine and triethylamine, inorganic bases such as sodium hydride and potassium carbonate, and alkali metal alkoxides such as potassium tert-butoxide. Can be mentioned.

The amount of the base used in the reaction is usually 1 to 10 mol, preferably 1 to 2 mol, per 1 mol of compound (VII).
The amount of compound (VI) to be subjected to the reaction is usually 1 to 10 mol, preferably 1 to 1.5 mol, per 1 mol of compound (VII).
The reaction temperature is usually in the range of −20 ° C. to the boiling point of the reaction solvent, and preferably in the range of 0 ° C. to room temperature.
The reaction time is, for example, 1 to 72 hours, preferably 1 to 24 hours.
After completion of the reaction, the target compound of the present invention can be isolated by performing post-treatment operations such as filtering the salt as it is, or pouring the reaction mixture into water, extracting with an organic solvent and concentrating. .
If necessary, it can be purified by chromatography, recrystallization or the like.

Manufacturing method 4
Compound (XI) of the present invention is obtained by reacting compound (IX) with compound (X) in the presence of a base.

In the formula, X represents a leaving group. As such a leaving group, for example, various leaving groups can be used without particular limitation as long as they are groups that are eliminated during the reaction. Preferable examples of such leaving groups include various leaving groups known to those skilled in the art such as halogen atoms and tosyl groups.
R ³ represents a C _{1 to} C ₃ alkyl group, a CH ₂ OR ² group, or a C (═O) OR ² group, and the range thereof is the same as in the case of R ¹ .
This reaction is usually performed in an inert solvent in the presence of a base. The inert solvent used in the reaction may be anything as long as it does not inhibit the reaction. For example, acid amides such as N-methylpyrrolidone and N, N-dimethylformamide, ethers such as tetrahydrofuran and diethyl ether, etc. Preferred examples include organic sulfurs such as dimethyl sulfoxide, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, and mixtures thereof.

Examples of the base used in the reaction include organic bases such as pyridine, 4-dimethylaminopyridine and triethylamine, inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide and potassium carbonate, potassium-tert Preferred examples include alkali metal alkoxides such as butoxide.
The amount of the base used in the reaction is usually 1 to 10 mol, preferably 1 to 2 mol, per 1 mol of compound (IX).
The amount of the compound (X) to be subjected to the reaction is usually 1 to 10 mol, preferably 1 to 2 mol, per 1 mol of the compound (IX).
The reaction temperature is usually in the range of −20 ° C. to the boiling point of the reaction solvent, and preferably in the range of 0 ° C. to the boiling point of the reaction solvent.
The reaction time is, for example, 1 to 72 hours, preferably 1 to 48 hours.
After completion of the reaction, the target compound of the present invention can be isolated by performing post-treatment operations such as filtering the salt as it is, or pouring the reaction mixture into water, extracting with an organic solvent and concentrating. .
If necessary, it can be purified by chromatography, recrystallization or the like.

Production method 5 (in formula (I), when substituent A is an R ² S group)
Compound (XV) is obtained by reacting compound (V) with compound (XII) in the presence of a base and then compound (XIII).

This reaction is usually carried out in an inert solvent in the presence of a base.
The inert solvent used in the reaction may be anything as long as it does not inhibit the reaction. For example, acid amides such as N-methylpyrrolidone and N, N-dimethylformamide, ethers such as tetrahydrofuran and diethyl ether, etc. Preferred examples include organic sulfurs such as dimethyl sulfoxide, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, and mixtures thereof. Preferable examples of the base used in the reaction include sodium hydride, inorganic bases such as potassium carbonate, and alkali metal alkoxides such as potassium tert-butoxide.
The amount of the base used in the reaction is usually 1 to 2 mol, preferably 1 to 1.2 mol, per 1 mol of compound (V). The amount of (XIII) used in the reaction is usually 1 to 10 mol, preferably 1 to 2 with respect to 1 mol of compound (V). The amount of (XII) used in the reaction is usually 1 to 2 moles, preferably 1 to 1.1 moles.
The reaction temperature is usually in the range of −10 ° C. to the boiling point of the reaction solvent, and preferably in the range of 0 ° C. to 50 ° C.
The reaction time is usually in the range of 1 to 72 hours, preferably in the range of 4 to 24 hours. After completion of the reaction, the target compound of the present invention can be isolated by post-treatment such as concentration as it is, or pouring the reaction mixture into water, extraction with an organic solvent and concentration.
Moreover, it can also refine | purify by chromatography, recrystallization, etc. as needed.

The amidine derivative of the present invention includes, for example, geometric isomers based on a double bond of a carbonylimino group (C═N) and tautomers based on N═C—NH— as follows. The invention includes any of these isomers.

（式中、ａを付した矢印は、Ｒ¹が、水素原子であることを示す。）

(In the formula, an arrow with a indicates that R ¹ is a hydrogen atom.)

The amidine derivatives of the present invention are useful as insecticides or acaricides. Therefore, the insecticide or acaricide using the amidine derivative of the present invention can be effectively applied to the following insects or mites.
Lepidopterous insect pests such as Spodoptera spp. Anemone, such as Rionetia spp., Stag beetles such as Japanese moths, Kibata such as cotton beetle, Hitrigas such as American white starfish, Hirosukoga such as iga, Koiga.

Hemiptera pests , leafhoppers, leafhoppers such as leafhoppers, leafhoppers such as leafhoppers and leafhoppers, aphids such as cotton aphids and aphids Whiteflies such as whiteflies, scale insects such as red beetle and ruby worms, firebirds, and lice.

Diptera pests , Culex mosquitoes, Chironomidae, House flies, House flies, Drosophila flies, etc. , Abu species, horn flies, leafhoppers, etc.
Coleoptera: Western corn root worms, Southern corn root worms, etc. Potato beetles, cucumber flea beetles, Colorado potato beetles, epiracunas such as beetles, nematode moth, etc., scallop beetles, moth beetles, longhorn beetles, blue beetle, etc.

Straight-eyed net insects such as German cockroaches, black cockroaches, American cockroaches, flying cockroaches, and cockroaches.
Thrips eye pests Southern thrips, Negia thrips, Hana thrips, etc.
Hymenopteran pests , hornets, scallops, wasps such as wasps, etc.
Straight- eye pests , grasshoppers, etc.

For example, anthropoid pest anemone flea.
Lice eye pests such as human lice and lice.
Isotope pests, such as Yamato termites and termites.

Acarid pests , such as spider mites, kanzawa spider mites, apple spider mites, apple spider mites, oligonicus spp. Ticks such as mites, shrimp ticks, mites such as mites, mites mites, mites, mites, mites, mites, mites, mites, etc.
Arachnid spiders, red spiders, etc.

Lips and leg nets , Tobisumkade, etc.
Double-legged nets , red-spotted, etc.
Such as Isopoda such Armadillidium vulgare.
Gastropod nettle, Japanese yellow slug

Nematodes: Southern Nematode Nematode, Northern Nematode Nematode, Soybean Cyst Nematode, Potato Cyst Nematode, Kita Neko Nematode, Sweet Potato Nematode, etc.
Furthermore, the trifluoromethylsulfonylamidine derivative of the present invention is also effective against pests that have developed resistance to existing insecticides.

The trifluoromethylsulfonylamidine derivative of the present invention is preferably blended, for example, in the range of 0.1 to 98% by mass, preferably 0.5 to 80% by mass in the preparation.
The trifluoromethylsulfonylamidine derivative of the present invention can be used in a pure form without adding other components when the amidine derivative of the present invention thus obtained is actually applied, and is intended for use as an agricultural chemical. Therefore, it can also be used in the form that can be taken by general agricultural chemicals, such as wettable powder, granules, powders, emulsions, aqueous solvents, suspensions, emulsions, solubilized preparations, liquids and the like.
When the trifluoromethylsulfonylamidine derivative of the present invention is sprayed, the concentration is, for example, 10 to 10,000 ppm, preferably 100 to 2,000 ppm.
In the present invention, as an additive and a carrier optionally blended in the preparation, when a solid agent is intended, vegetable powders such as soybean husk grains, wheat flour, walnut husk grains, diatomaceous earth, and limestone Organic and inorganic compounds such as mineral powders such as gypsum, charcoal cal, talc, bentonite, pyrophyllite, clay, sulfates, phosphates, urea, mirabilite, sugars, and water-soluble polymer powders are used. The

For liquid dosage forms, petroleum fractions such as kerosene, chelesin, solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, xylyl xylene mineral oil Vegetable oil, water, etc. are used as solvents.
In order to take a uniform and safe form in these preparations, it is useful to add a surfactant or other auxiliary agent if necessary. The amount of the active ingredient is generally 0.1 to 90%, preferably 0.5 to 70%, based on the mass of each active ingredient.
The wettable powder, emulsion, suspension, emulsion, and the like thus obtained are diluted with water to a predetermined concentration, and the powder or granule is used as it is by a general spraying method. Is done.
The preparation thus obtained can be used as it is or diluted with water or the like.
Also, mixed with other commercially available insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feeds, etc., or By using them simultaneously without mixing, the application range can be expanded and labor saving can be achieved.

Hereinafter, the present invention will be described in more detail with reference to Examples, Formulation Examples and Test Examples, but the scope of the present invention is not limited by these Examples and the like.
First, preparation of the amidine derivative of the present invention will be described.

Example 1
Preparation of N- (3,5-bis (trifluoromethyl) phenyl) -N ′-(trifluoromethylsulfonyl) -isopropylcarboxyimidamide (Compound 12) 3,5-bis-trifluoromethylaniline 1 in 10 ml of tetrahydrofuran .3 g and 1.0 g of triethylamine were dissolved, and 1.2 g of N- (trifluoromethylsulfonyl) isobutylimidoyl chloride was added with stirring under ice cooling. After returning to room temperature, the reaction mixture was stirred until completion of the reaction, triethylamine hydrochloride was filtered off, and the residue was concentrated. The obtained crude product was subjected to silica gel column chromatography to obtain 0.6 g of the desired product.
1H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 1.42 (d, d, 6H), 3.40 (m, 1H), 8.03 (s, 1H), 8. 22 (s, 2H), 10.91 (s, 1H)
m. p. (161-163 ° C)

Example 2
Preparation of N- (2,4,6-trichlorophenyl) -N ′-(trifluoromethylsulfonyl) -cyclopropanecarboxyimidamide (Compound 30) 0.9 g of 2,4,6-trichloroaniline in 10 ml of tetrahydrofuran, triethylamine 0.5 g was dissolved, and 1.0 g of N- (trifluoromethylsulfonyl) cyclopropanecarboximidoyl chloride was added with stirring under ice cooling. After returning to room temperature, the reaction mixture was stirred until completion of the reaction, triethylamine hydrochloride was filtered off, and the residue was concentrated. The obtained crude product was subjected to silica gel column chromatography to obtain 0.4 g of the desired product.
1H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 1.00-1.43 (m, 4H), 2.50-2.56 (m, 1H), 7.87 (s 2H), 10.51 (s, 1H)
m. p. (160-161 ° C)

Example 3
Production of N- (3,5-bis (trifluoromethyl) phenyl) -N ′-(trifluoromethylsulfonyl) -O-isopropyl-isourea (Compound 65) 0.15 g of isopropyl alcohol and 0.29 g of triethylamine in 10 ml of tetrahydrofuran Then, 1.0 g of N- (3,5-bis (trifluoromethyl) phenylamino-chloromethylene) -trifluoromethanesulfonamide was added with stirring under ice cooling. After returning to room temperature, the reaction mixture was stirred until completion of the reaction, triethylamine hydrochloride was filtered off, and the residue was concentrated. The obtained crude product was subjected to silica gel column chromatography to obtain 0.7 g of the desired product.
1H-NMR (300 MHz, CDCl _{3 /} TMS): σ (ppm) = 1.33 (dd, 6H), 5.32 (m, 1H), 7.64-7.74 (m, 3H), 9. 29 (s, 1H)

Example 4
Preparation of N- (3,5-bis (trifluoromethyl) phenyl) -N ′-(trifluoromethylsulfonyl) -S-methyl-isothiourea (Compound 67) 0.55 g of trifluoromethanesulfonamide was dissolved in 10 ml of tetrahydrofuran. Then, 0.5 g of potassium t-butoxide was added with stirring at room temperature. After stirring at room temperature for 30 minutes, 1.0 g of 3,5-bis (trifluoromethyl) phenyl isothiocyanate was added, and the mixture was stirred at room temperature for 1 hour and further at 50 ° C. for 30 minutes. After returning the reaction solution to room temperature, 0.68 g of methyl iodide was added dropwise and stirred at room temperature for one day. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain 0.8 g of the desired product.
1H-NMR (300 MHz, CDCl _{3 /} TMS): σ (ppm) = 1.33 (dd, 6H), 5.32 (m, 1H), 7.64-7.74 (m, 3H), 9. 29 (s, 1H)
m. p. (94-95 ° C)

  Examples 1 to 4 and examples of compounds represented by the general formula (I) produced in the same manner are shown in the table. However, the present invention is not limited to these. In the table, n- is normal, i- is iso-, s is secondary, t- is tertiary, c- is cyclo, Me is methyl, Et is ethyl, Pr represents propyl and Bu represents butyl.

表１

Table 1

Table 1 (continued)

Table 1 (continued)

1H-NMR data
Compound No. 15
1H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 1.40 (d, 6H), 3.40-3.45 (m, 1H), 7.50 (s, 2H), 7.86 (s, 1H), 10.91 (s, 1H)
Compound No. 65
1H-NMR (300 MHz, CDCl _{3 /} TMS): σ (ppm) = 1.33 (dd, 6H), 5.32 (m, 1H), 7.64-7.74 (m, 3H), 9. 29 (s, 1H)
Compound No. 66
1H-NMR (300 MHz, CDCl _{3 /} TMS): σ (ppm) = 2.49 (s, 3H), 7.79 (s, 2H), 7.94 (s, 1H), 9.69 (bs, 1H)

Next, formulation examples of the amidine derivative of the present invention are shown. In addition, a part represents a mass part.
Formulation Example 1 (wettable powder)
Compound 2, 50 parts, lignin sulfonate 3 parts, sodium lauryl sulfate 2 parts, synthetic hydrous silicic acid 10 parts and clay 35 parts finely pulverized to an average particle size of 10 μm with a hammer mill were mixed well, and then pulverized with a jet mill. Each wettable powder was obtained.
Formulation Example 2 (Emulsion)
Each emulsion was obtained by uniformly dissolving 10 parts of Compound 12, 9 parts of polyoxyethylene styrenated phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 20 parts of N-methylpyrrolidone and 55 parts of xylene.

Formulation Example 3 (Granule)
After adding 13 parts of sodium lignin sulfonate, 1 part of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 61 parts of clay to 5 parts of compound 13 finely pulverized with a hammer mill to an average particle size of 10 μm, the mixture is thoroughly stirred and mixed with a ribbon mixer. Then, an appropriate amount of water is added to these mixtures, further kneaded, granulated with an extrusion granulator (screen hole: 0.8 mm), dried by ventilation, and then granulated and sieved to obtain each granule.

Formulation Example 4 (powder)
30 parts of compound 30 finely pulverized to an average particle size of 8 μm with a hammer mill, 5 parts of synthetic hydrous silicic acid, 0.3 part of PAP and 93.7 parts of clay were added and stirred and mixed with a pin mill to obtain each powder.

Formulation Example 5 (Flowable)
Compound 48, 20 parts finely pulverized to an average particle size of 8 μm with a hammer mill, 7 parts of polyoxyethylene styrene styrenated phenyl ether phosphate ammonium salt, 0.2 part of silicon antifoaming agent and 22.8 parts of water were added, and a mixer And a dispersion was obtained. After finely pulverizing this dispersion to an average particle size of 1.5 μm with a bead mill, 40 parts of an aqueous solution containing 0.5 part of xanthan gum and 0.2 part of preservative is added thereto, and 10 parts of propylene glycol is further added. And gently stirring and mixing to obtain each 10% flowable agent.

  Next, it is shown by test examples that the amidine derivative of the present invention is useful as an active ingredient of an insecticide or an acaricide. In addition, the amidine derivative of this invention is shown by the compound number as described in a table | surface, and the compound used for the comparison control is shown by the compound A shown below.

Comparative compound A: Compound No. 58 described in JP-A-56-26803

Test Example 1 (Insecticidal test against Spodoptera litura)
Each emulsion of the compound obtained according to Formulation Example 2 was diluted with water so that the active ingredient concentration was 500 ppm. The water dilution obtained was sprayed on 6-7 leaf Chinese cabbage leaves and air-dried, then placed in a plastic container of length 21 cm x width 13 cm x depth 3 cm. The head was released. The lid was covered and left in a constant temperature room at 26 ° C., and the number of live and dead insects after 48 hours was examined to determine the death rate. The results are shown in Table 2 below.

Table 2

Test Example 2 (Acaricidal test for Kanzawa spider mite)
A glass disk with a hole (diameter 12 cm) was placed on a styrene cup containing water, and a filter paper (diameter 11 cm) was placed on the finely cut cotton and dampened. A leaf disc of primary green beans cut into 5 cm long and 2.5 cm wide was placed on a damp filter paper, and 10 adult female Tetranychus kanzawai were released. After standing in a 26 ° C. incubator for 1 day, each emulsion of the compound obtained according to Formulation Example 2 was diluted with water so that the active ingredient concentration was 500 ppm. The obtained water dilution was spread on a leaf disk, air-dried, and returned to the 26 ° C. incubator. The number of adult mortality 24 hours after spraying was examined to determine the adult mortality rate.
Furthermore, after investigating the mortality rate of adults, spider mites on leaf discs were removed with a small brush, and returned to a 26 ° C. incubator and allowed to stand. Seven days after spraying, the number of unhatched eggs and the number of live and dead larvae were investigated, and the ratio of unhatched eggs and hatched larvae were determined. The results are shown in Table 3 below.

※表中、ふ化幼虫死虫率の−は殺卵率１００％を示す。 Table 3

* In the table,-of the hatched larvae mortality rate indicates an egg killing rate of 100%.

Test Example 3 (Insecticidal test against leafhopper leafhopper)
Each emulsion of the compound obtained according to Formulation Example 2 was diluted with water so that the active ingredient was 500 ppm. Bunch five rice seedlings of 1.5 to 2 leaf age in the resulting diluted solution, soak for 10 seconds, and after air drying, place them in a test tube with a length of 20 cm and a diameter of 2.5 cm, and the age of Nephotettix cinceticeps is 3 years old. Ten larvae were released. The lid was covered and left in a constant temperature chamber at 26 ° C., and the number of live and dead insects after 48 hours was examined to determine the death rate. The results are shown in Table 4 below.












Table 4

  As can be seen from the above test examples, the trifluoromethylsulfonylamidine derivative of the present invention has an excellent insecticidal effect and acaricidal effect. Therefore, an insecticide or acaricide can be produced using the amidine derivative of the present invention.

Claims (10)

Formula (I)

(Where
A represents a C ₁ -C ₅ alkyl group, a C ₃ -C ₅ cycloalkyl group, an OR ² group, an NHR ² group or an SR ² group,
R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group or a C (═O) OR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
A trifluoromethylsulfonylamidine derivative represented by: Wherein A is, trifluoromethylsulfonyl amidine derivative according to claim 1 is a C ₁ -C ₃ alkyl or C ₃ -C ₅ cycloalkyl group.   The trifluoromethylsulfonylamidine derivative according to claim 1, wherein B is a halogen atom or a trifluoromethyl group. Formula (II)

(Where
A represents a C ₁ -C ₅ alkyl or C ₃ -C ₅ cycloalkyl group. )
A compound represented by
Formula (III)

(Where
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
m represents an arbitrary integer of 1 to 5,
R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group or a C (═O) OR ² group,
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
However, when a plurality of B are present, they may be the same or different. )
A compound represented by
The method for producing a trifluoromethylsulfonylamidine derivative according to claim 1, wherein the reaction is carried out in the presence of a base. Formula (IV)

(Where
A represents a C ₁ -C ₅ alkyl or C ₃ -C ₅ cycloalkyl group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
A compound represented by
The following formula (V),

A compound represented by
The method for producing a trifluoromethylsulfonylamidine derivative according to claim 1, wherein the reaction is carried out in the presence of a base. Formula (VI)

(Where
R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group or a C (═O) OR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
A compound represented by
Formula (VII)

(Where
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
Y represents an NH ₂ group, an SH group or an OH group. )
A compound represented by
In the presence of a base,
Formula (VIII)

(Where
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
Z represents an NH group, a sulfur atom, or an oxygen atom. )
The manufacturing method of the trifluoromethylsulfonylamidine derivative represented by these. Formula (IX)

(Where
A represents a C ₁ -C ₅ alkyl group, a C ₃ -C ₅ cycloalkyl group, an OR ² group, an NHR ² group or an SR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
A compound represented by
The following formula (X),

(Where
R ³ represents a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group or a C (═O) OR ² group,
X represents a leaving group. )
A compound represented by
In the presence of a base,
The following formula (XI),

(Where
A represents a C ₁ -C ₅ alkyl group, a C ₃ -C ₅ cycloalkyl group, an OR ² group, an NHR ² group or an SR ² group,
R ³ represents a C ₁ -C ₃ alkyl group, a CH ₂ OR ² group or a C (═O) OR ² group,
B represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
R ² represents a C ₁ -C ₃ alkyl group or a cycloalkyl group,
m represents an arbitrary integer of 1 to 5,
However, when a plurality of B are present, they may be the same or different. )
The manufacturing method of the trifluoromethylsulfonylamidine derivative shown by these.   An insecticide or acaricide containing the trifluoromethylsulfonylamidine derivative according to claim 1 as an active ingredient.   An insecticide or acaricide containing the trifluoromethylsulfonylamidine derivative according to claim 2 as an active ingredient.   An insecticide or acaricide containing the trifluoromethylsulfonylamidine derivative according to claim 3 as an active ingredient.