JP2006117565A - Trifluoromethylsulfonylamidine derivative effective in controlling noxious organism - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound effective in insecticidal or acaricidal action. <P>SOLUTION: The compound provided is a trifluoromethylsulfonylamidine derivative represented by formula (1) (wherein A and B are each a hydrogen atom, a halogen atom, a 1-6C alkyl group, a 1-6C haloalkyl group, a 1-6C alkoxy group, a 1-6C haloalkoxy group, a 1-3C alkylthio group, a 1-3C haloalkylthio group, a 1-3C alkylsulfinyl group, a 1-3C haloalkylsulfinyl group, a 1-3C alkylsulfonyl group, a 1-3C haloalkylsulfonyl group, a nitro group, or a cyano group, provided that when two or more A's or B's are present, they may be the same with or different from each other; and m and n are each an optional integer of 1-5). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

Conventionally, various pesticides such as insecticides have been studied. For example, JP-A-56-22704, JP-A-5-1034, and JP-A-6-293738 disclose pest control agents using amidine compounds.
However, Japanese Patent Application Laid-Open No. 56-22704 relates to an agricultural and horticultural fungicide, and the amino nitrogen substituent in the amidine bond does not contain a phenyl group, and is a carbonylimino group (C = N). No trifluoromethylsulfonyl group is disclosed as a nitrogen substituent.
JP-A-5-1034 discloses amidine derivatives used for insecticides, but no phenyl group is mentioned as the carbon atom substituent of the carbonylimino group. No trifluoromethylsulfonyl group is mentioned as a nitrogen substituent.
Further, JP-A-6-293381 relates to a herbicide, and relates to a compound having a nitrogen-containing heterocyclic group which is greatly different from a trifluoromethylsulfonyl group as a nitrogen substituent of a carbonylimino group. No mention is made of a phenyl group as a substituent.

On the other hand, Japanese Patent Application Laid-Open No. 57-156407, Japanese Patent Publication No. 63-24483, and Japanese Patent Application Laid-Open No. 10-218857 disclose pest control agents having a trifluoromethylsulfonamide group.
However, Japanese Patent Application Laid-Open No. 57-156407 and Japanese Patent Publication No. 63-24483 relate to insecticides and acaricides, but do not have amidine bonds and merely disclose sulfonamide compounds.
Japanese Patent Laid-Open No. 10-218857 discloses a compound used as an indoor dust mite control agent, but does not have an amidine bond, but merely discloses a sulfonamide compound.
Furthermore, J. Chem. Soc., Perkin Trans. 2, 2002, 1950-1955 discloses an amidine compound having a trifluoromethylsulfonyl group, but there is no description about its use, and in addition, in amidine binding. No phenyl group is disclosed as a substituent on the amino nitrogen.

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. And the present invention has been achieved.
That is, the present invention relates to the following inventions.
1. The following formula (I),

(I)

(I)

A trifluoromethylsulfonylamidine derivative represented by:
(Where
A and B are same with or may be different, a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ halo alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ haloalkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ haloalkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ ~ C _{3 represents a} haloalkylsulfonyl group, a nitro group, or a cyano group,
m and n represent any integer of 1 to 5,
However, when there are a plurality of A or B, they may be the same or different. )

2. Formula (II)

(II)

(II)

(In the formula, A and m represent the same meaning as described above.)
A compound represented by
Formula (III)

(III)

(III)

(In the formula, B and n represent the same meaning as described above.)
A compound represented by
In the presence of a base, a process for producing a trifluoromethylsulfonylamidine derivative represented by the formula (I).
3. Formula (IV)

(IV)

(IV)

(A, B, m and n represent the same meaning as described above.)
A compound represented by
The following formula (V),

(Ｖ)

(V)

(In the formula, X represents a leaving group.)
A compound represented by
A method for producing a trifluoromethylsulfonylamidine derivative represented by the formula (I), wherein the reaction is carried out in the presence or absence of a base.
4). The following formula (VI),

(VI)

(VI)

(A, B, m and n represent the same meaning as described above.)
A compound represented by
Formula (VII)

(VII)

(VII)

A compound represented by
In the presence of a base, a process for producing a trifluoromethylsulfonylamidine derivative represented by the formula (I).
5. An insecticide or acaricide containing the trifluoromethylsulfonylamidine derivative described in 1 above as an active ingredient.

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

Hereinafter, the present invention will be described in detail.
The amidine derivative pair of the present invention is a compound having a structure represented by the above formula (I).
In the above formula, A or B is a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ haloalkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ haloalkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₃ haloalkylsulfonyl group , A nitro group, or a cyano group.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The C ₁ -C ₆ alkyl group, e.g., methyl group, ethyl group, n- propyl group, iso- propyl, n- butyl, iso- butyl group, sec- butyl group, tert- butyl group, n- A pentyl group and n-hexyl group are mentioned, Preferably a methyl group etc. are mentioned.
Examples of the C ₁ -C ₆ haloalkyl group include a chloromethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a perfluoro-iso-propyl group, and a perfluoro-n-butyl group. Perfluoro-n-pentyl group and perfluoro-n-hexyl group, preferably trifluoromethyl group, perfluoro-iso-propyl group, perfluoro-n-butyl group and the like.
The C ₁ -C ₆ alkoxy group, for example, a methoxy group, an ethoxy group, n- propyl group, n- butyloxy, n- pentyloxy group, and n- hexyl group, preferably a methoxy group Etc.

Examples of the C ₁ -C ₆ haloalkoxy group include a trifluoromethoxy group, a bromodifluoromethoxy group, a difluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propyloxy group, and a perfluoro-iso-propyloxy group. Perfluoro-n-butyloxy group, perfluoro-n-pentyloxy group, perfluoro-n-hexyloxy group, preferably trifluoromethoxy group.
The C ₁ -C ₃ alkylthio group, for example, methylthio group, ethylthio group, n- propylthio group, iso- propylthio group, and preferably a methylthio group and the like.
Examples of the C ₁ -C ₃ haloalkylthio group include a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, a perfluoroethylthio group, a 1H, 1H-perfluoro-n-propylthio group, A perfluoro-n-propylthio group and a perfluoro-iso-propylthio group are exemplified, and a trifluoromethylthio group and the like are preferable.

The C ₁ -C ₃ alkylsulfinyl group, for example, methylsulfinyl group, ethylsulfinyl group, n- propyl sulfinyl groups include iso- propyl sulfinyl group, preferably and the like methylsulfinyl group.
Examples of the C ₁ -C ₃ haloalkylsulfinyl group include a trifluoromethylsulfinyl group, a 2,2,2-trifluoroethylsulfinyl group, a perfluoroethylsulfinyl group, and a 1H, 1H-perfluoro-n-propylsulfinyl group. Perfluoro-n-propylsulfinyl group and perfluoro-iso-propylsulfinyl group, preferably trifluoromethylsulfinyl group.
The C ₁ -C ₃ alkylsulfonyl group, for example, methylsulfonyl group, ethylsulfonyl group, n- propylsulfonyl group, and iso- propylsulfonyl group, preferably such as a methyl sulfonyl group.

The C ₁ -C ₃ haloalkylsulfonyl group, e.g., trifluoromethylsulfonyl group, 2,2,2-trifluoroethyl sulfonyl group, perfluoroethylsulfonyl group, IH, 1H-perfluoro -n- propylsulfonyl group, Examples include a perfluoro-n-propylsulfonyl group and a perfluoro-iso-propylsulfonyl group, preferably a trifluoromethylsulfonyl group.
The leaving group is not particularly limited as long as it is a group capable of leaving during the reaction, and various known leaving groups can be used. For example, a functional group such as a halogen atom or a trifluoromethanesulfonyloxy group is preferable. Can be listed.

  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 method 1, production method 2 or production method 3. Unless otherwise specified, the symbols in the formula have the above meanings.

Manufacturing method 1
(Process 1)
Compound (IV) is obtained by reacting the following compound (VIII) with the following compound (III), and then the obtained compound (IV) is reacted with compound (V) in the presence of a base. Thus, the compound (I) of the present invention is obtained.

Many known methods are known for the reaction, and can be produced by referring to various books and literatures. For example, New Experimental Chemistry Course 14-IIIpp1608-1621, Chem. Commun., 1971, 498-499, Bull. Soc. Chim. Fr., 1970,200, Org. Synth., IV, 769 (1963).
When a base catalyst is used for the reaction, examples of the base include inorganic bases such as sodium hydride.
The reaction temperature is, for example, −40 ° C. to the boiling point of the reaction solvent, preferably 0 ° C. to room temperature.
After completion of the reaction, for example, compound [IV] can be isolated by putting the reaction solution into ice-cold water and collecting the precipitated solid by filtration. Moreover, it can also refine | purify by chromatography, recrystallization, etc. as needed.

When an acid catalyst is used for the reaction, examples of the acid include Lewis acids such as aluminum chloride.
Reaction temperature is 100 to 250 degreeC, for example, Preferably, it is the range of 150 to 200 degreeC.
After completion of the reaction, for example, the compound [IV] can be isolated by charging the reaction solution into an alkaline aqueous solution and collecting the precipitated solid by filtration. Moreover, it can also refine | purify by chromatography, recrystallization, etc. as needed.

(Process 2)
The 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 in the reaction include pyridine, organic bases such as 4-dimethylaminopyridine and triethylamine, inorganic bases such as potassium carbonate, and alkali metal alkoxides such as potassium tert-butoxide.
The amount of the base is usually 1 to 10 mol, preferably 1 to 2 mol, per 1 mol of compound (IV).
The amount of the compound (V) to be subjected to the reaction is usually 1 to 10 mol, preferably 1 to 2 mol, relative to 1 mol of the compound (IV).
The reaction temperature is usually from −20 ° C. to the boiling point of the reaction solvent, and preferably from 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 salt is filtered and then concentrated as it is, or the reaction mixture is poured into water, followed by post-treatment such as extraction with an organic solvent and concentration to isolate the compound represented by the formula (I). Can do. If necessary, it can be purified by chromatography, recrystallization or the like.

Manufacturing method 2
Compound (IX) and compound (VII) are reacted in the presence of a base to obtain compound (X). Further, the resulting compound (X) is reacted with a halogenating agent to give compound (II). And is reacted with compound (III) in the presence of a base to give compound (I) of the present invention.

Furthermore, it demonstrates in detail.
(Process 1)
The 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 in the reaction include organic bases such as triethylamine, and inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, and potassium carbonate.

The amount of the base used in the reaction is usually 1 to 10 mol, preferably 2 to 3 mol, per 1 mol of compound (VII). The amount of compound (IX) to be subjected to the reaction is usually 1 to 10 mol, preferably 1 to 2 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 salt can be filtered and concentrated, and the resulting oil or solid can be treated with sulfuric acid, hydrochloric acid or the like to isolate compound (X). If necessary, it can be purified by chromatography, recrystallization or the like. Further, it can be produced by, for example, Eur. J. Org., Chem. 2001, 1225-1233, US Pat. No. 3,637,845 or a method analogous thereto.

(Process 2)
The reaction can be usually produced by a reaction with a halogenating agent in a solvent.
Examples of the halogenating agent include phosphorus pentachloride, phosphorus oxychloride, Vilsmeier reagent prepared from phosphorus oxychloride and dimethylformamide, and the like.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as toluene and xylene, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, and the like. Examples thereof include halogenated hydrocarbons, ethers such as diisopropyl ether, dioxane, and tetrahydrofuran, and mixtures thereof. Alternatively, the halogenating agent can be used as a solvent as it is.
The reaction temperature is usually in the range of −5 ° C. to the boiling point of the reaction solvent, preferably in the range of room temperature to the boiling point of the reaction solvent.
The reaction time is usually 10 minutes to 72 hours, preferably 1 to 6 hours.
After completion of the reaction, the desired product can be obtained by an operation such as distillation.
Further, for example, it can be produced by Eur. J. Org., Chem. 2001, 1225-1233, or a method according thereto.

(Process 3)
The 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. Examples thereof include acid amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, and organic substances such as dimethyl sulfoxide. Examples thereof include aromatic hydrocarbons such as sulfur and toluene, halogenated hydrocarbons such as dichloromethane, and mixtures thereof.
Examples of the base used in the reaction include pyridine, organic bases such as 4-dimethylaminopyridine and triethylamine, and inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide and potassium carbonate.

The amount of the base is usually 1 to 10 mol, preferably 1 to 2 mol, per 1 mol of compound (II).
The amount of compound (III) to be subjected to the reaction is usually 1 to 10 mol, preferably 1 to 1.5 mol, per 1 mol of compound (II).
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 3
Compound (IX) and compound (III) are reacted in the presence or absence of a base to obtain compound (XI), and further a halogenating agent is reacted with the obtained compound (XI). Compound (I) is obtained by reacting the obtained compound (VI) with compound (VII) in the presence of a base.

(Process 1)
The reaction is usually performed in an inert solvent in the presence or absence 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 in the reaction as needed include pyridine, organic bases such as 4-dimethylaminopyridine and triethylamine, and inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide and potassium carbonate. 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 (III).
The amount of compound (IX) to be subjected to the reaction is usually 1 to 10 mol, preferably 1 to 1.2 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, for example, 1 to 72 hours, preferably 1 to 24 hours.
After completion of the reaction, the compound (XI) can be isolated by performing post-treatment operations such as concentration after filtration of the salt, or pouring of the reaction mixture into water, extraction with an organic solvent, and concentration. If necessary, it can be purified by chromatography, recrystallization or the like.

(Process 2)
This reaction can be usually produced by a reaction with a halogenating agent in a solvent. Examples of the halogenating agent used in the reaction include phosphorus pentachloride, phosphorus oxychloride, Vilsmeier reagent prepared from phosphorus oxychloride and dimethylformamide, and the like.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as toluene and xylene, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, and the like. Examples thereof include halogenated hydrocarbons, ethers such as diisopropyl ether, dioxane, and tetrahydrofuran, and mixtures thereof, or a rominating agent can be used as a solvent as it is.
The reaction temperature is usually in the range of −5 ° C. to the boiling point of the reaction solvent, preferably in the range of room temperature to the boiling point of the reaction solvent.
The reaction time is usually 10 minutes to 72 hours, preferably 30 minutes to 6 hours.
After completion of the reaction, the desired product can be obtained by an operation such as distillation.
Further, for example, Eur. J. Org., Chem. 2001, 1225-1233, JP-A-2001-342170, J. Org., Chem. 1981, 46, 608-610, JCS Perkin II, 1980, 1318- 1325, J. Heterocyclic chem., 1992, 29, 703-706, J. Org. Chem. 1992, 57, 196-201, US 2003-0040521, or a method analogous thereto. .

(Process 3)
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 in the reaction include pyridine, organic bases such as 4-dimethylaminopyridine and triethylamine, 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 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.

  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.

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 pests <br/> Sinkiga, such as the genus Lionettia, Suga, Shirasu, Swordfish, such as cotton beetle, Hitriga, such as American white starfish, Hirosukoga, such as iga, Koiga.

Hemiptera pest <br/> Leafhoppers such as Japanese brown planthopper, yellow planthopper, white-tailed planthopper, leafhoppers such as leafhoppers, leafhoppers, and aphids such as cotton aphids and aphids Whitefly whitefly, silver leaf whitefly, and other scale insects such as red beetle, ruby worm, bug, and whitefly.

Dipterous pests <br/> house mosquitoes such as mosquitoes, mosquitoes, house moths, house flies, house flies, etc. Butterflies, flyfish, fly, sand flies, leafhoppers, etc.
Coleoptera <br/> Western corn root worm, Southern corn root worm, etc. Corn root worms, Dougane buoy, scarab beetle etc. Ganoderma beetles such as beetle, potato beetle, potato beetle, beetle such as Colorado beetle;

Straight-eyed net insect pests such as German cockroaches, black cockroaches, American cockroaches, flying cockroaches, and cockroaches.
Thrips pest <br/> Southern thrips, Negia thrips, Hana thrips, etc.
Hymenoptera pests , bees such as ants, wasps, scallops, wasps, etc.
Straight-eyed pests <br/> Kera, grasshoppers, etc.

Lepidoptera pests such as human fleas.

Lice pests such as human lice and lice.
Isoptera pests Yamato termites, house termites, etc.

Mite spiders <br/> Ticks such as ticks, yamatoid mites, shrimp ticks, ticks, mites such as mites, mites, mites, mites, mites, mites, mites, etc. ), Spiders (eg, birch spiders, red spiders).

Lip and leg nets <br/>
Double leg nets <br/>
Such as Isopoda such <br/> Armadillidium vulgare.
Belly foot network such <br/> Chaco slug, such as Yellow Kou La slugs.

Nematodes <br/> Southern Nematode, Kitanegusu Nematode, Soybean Cyst Nematode, Potato Cyst Nematode, Flycatcher Nematode, Sweet Root Nematode, etc.

The amidine derivatives of the present invention are also effective against pests that have developed resistance to existing insecticides. When the amidine derivative of the present invention thus obtained is actually applied, it can be used in a pure form without adding other components. For the purpose of use as an agrochemical, a form that can be taken by a general agrochemical, for example, , Wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, emulsions, solubilized preparations, liquids and the like.
Additives and carriers, for solid preparations, vegetable powders such as soybean hulls, wheat flour, walnut hulls, diatomaceous earth, limestone, gypsum, charcoal cal, talc, bentonite, pyrophyllite Organic and inorganic compounds such as mineral fine powders such as clay, sulfates, phosphates, urea, mirabilite, saccharides, and water-soluble polymer powders are used.

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. 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 ′-((trifluoromethyl) sulfonyl) -4-chlorobenzenecarboximidamide (Compound 8) N- (3,5- Bis (trifluoromethyl) phenyl) -4-chlorobenzenecarboxyimidamide (2.0 g) and pyridine (0.8 g) were dissolved, and trifluoromethanesulfonyl chloride (1.2 g) was added dropwise under ice-cooling and stirring. After completion of the dropwise addition, the mixture was returned to room temperature and stirred overnight. Water was added to the reaction mixture, and the mixture was extracted with dichloromethane, washed with dilute hydrochloric acid, water and saturated brine, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was subjected to silica gel column chromatography to obtain 0.6 g of the desired product.
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 11.37 (s, 1H), 8.48 (s, 2H), 7.93 (s, 1H), 7.86 (Dd, 2H), 7.72 (dd, 2H)
m. p. (57-59 ° C)

Example 2
Production of N- (3,5-bis (trifluoromethyl) phenyl) -N ′-((trifluoromethyl) sulfonyl) -4-chlorobenzenecarboximidamide (Compound 9) (Isomer of Compound 8)
0.8 g of 3,5-bis-trifluoromethylaniline and 0.4 g of triethylamine were dissolved in 10 ml of tetrahydrofuran, and 1.0 g of 4-chloro-N- (trifluoromethylsulfonyl) benzimidoyl 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 1.1 g of the desired product.
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 12.03 (s, 1H), 8.29 (s, 2H), 8.02 (s, 1H), 7.80 (Dd, 2H), 7.71 (dd, 2H)
m. p. (186-187 ° C)
Example 3 (Another method of Example 2)
Production of N- (3,5-bis (trifluoromethyl) phenyl) -N ′-((trifluoromethyl) sulfonyl) -4-chlorobenzenecarboximidamide (Compound 9) (Isomer of Compound 8)
In 10 ml of tetrahydrofuran, 0.3 g of trifluoromethanesulfonamide, 0.6 g of triethylamine, and 0.1 g of 4- (N, N-dimethylamino) pyridine are dissolved, and 4-chloro-N- (3,5-bis is stirred at room temperature. 1.0 g of (trifluoromethyl) phenyl) benzimidoyl chloride was added. The mixture was stirred at room temperature 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 0.5 g of the desired product.
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 12.00 (s, 1H), 8.31 (s, 2H), 8.06 (s, 1H), 7.84 (Dd, 2H), 7.73 (dd, 2H)
m. p. (186-187 ° C)

Example 4
Preparation of N- (3,5-bis (trifluoromethyl) phenyl) -N ′-((trifluoromethyl) sulfonyl) -4-iodobenzenecarboximidamide (Compound 18) 3,5-bis- 1.8 g of trifluoromethylaniline and 1.5 g of triethylamine were dissolved, and 3.0 g of 4-iodo-N- (trifluoromethylsulfonyl) benzimidoyl 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 1.6 g of the desired product.
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 11.97 (s, 1H), 8.29 (s, 2H), 8.06 (s, 1H), 8.01 (Dd, 2H), 7.60 (dd, 2H)
m. p. (219-220 ° C)

Example 5
Preparation of N- (2,6-dimethyl-4- (perfluoroisopropyl) phenyl) -N ′-((trifluoromethyl) sulfonyl) -4-chlorobenzenecarboximidamide (Compound 47) 2,6- 1.5 g of dimethyl-4- (perfluoroisopropyl) aniline and 0.7 g of triethylamine were dissolved, and 1.5 g of 4-chloro-N- (trifluoromethylsulfonyl) benzimidoyl 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 1.0 g of the desired product.
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 11.56 (s, 1H), 7.87-7.71 (m, 4H), 7.49 (s, 2H) 2.31 (s, 6H)
m. p. (191-192 ° C)

Example 6
Preparation of N- (4-chlorophenyl) -N ′-((trifluoromethyl) sulfonyl) -3,5-bis-trifluoromethylbenzenecarboxyimidamide (Compound 11) 0.49 g of 4-chloroaniline in 20 ml of tetrahydrofuran, 0.48 g of triethylamine was dissolved, and 1.5 g of 3,5-bis-trifluoromethyl-N- (trifluoromethylsulfonyl) benzimidoyl 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 1.54 g of the desired product.
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 11.94 (s, 1H), 8.55 (s, 2H), 8.46 (s, 1H), 7.68 -7.57 (m, 4H)
m. p. (122-124 ° C)

  Examples 1 to 6 and examples of the 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- represents normal-, iso- represents iso-, and tert- represents tertiary.

(I)

(I)

¹ H-NMR data
Compound No. 7
¹ H-NMR (300 MHz, CDCl _{3 /} TMS): σ (ppm) = 8.06, 8.14 (ss, 1H), 7.80-7.40 (m, 7H)
Compound No. 14
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 11.41 (s, 1H), 8.38-8.00 (m, 6H)
Compound No. 16
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 12.77 (s, 1H), 8.63 (s, 1H), 8.28 (s, 2H), 8.15 -8.11 (m, 3H)

Compound No. 22
¹ H-NMR (300 MHz, CDCl _{3 /} TMS): σ (ppm) = 8.1 (s, 1H), 7.98-7.71 (m, 7H)
Compound No. 33
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 18.55 (s, 1H), 8.31 (s, 2H), 8.04 (s, 1H), 7.75 (Dd, 2H), 7.48 (dd, 2H), 2.56 (s, 3H)
Compound No. 36
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 12.55 (s, 1H), 8.60 (s, 2H), 8.52 (s, 1H), 8.29 (S, 2H), 8.14 (s, 1H)
Compound No. 59
¹ H-NMR (300 MHz, DMSO-d _{6 /} TMS): σ (ppm) = 8.48 (s, 1H), 8.28 (d, 1H), 7.93 (d, 1H), 7.80 -7.70 (m, 4H)

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 56, 50 parts finely pulverized to an average particle size of 10 μm with a hammer mill, 3 parts of sodium lignin sulfonate, 2 parts of sodium lauryl sulfate, 10 parts of synthetic hydrous silicic acid and 35 parts of clay 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 47, 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)
Compound 48 finely pulverized to an average particle size of 10 μm with a hammer mill, 3 parts of sodium lignin sulfonate, 1 part of sodium dodecylbenzene sulfonate, 30 parts of bentonite and 61 parts of clay were added and mixed thoroughly 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)
Compound 67 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 mixed by stirring with a pin mill to obtain each powder.

Formulation Example 5 (Flowable)
Add 9 to 20 parts of compound 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, and 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. 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.

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 resulting aqueous diluted solution was dried sparged wind cabbage leaves 6-7 leaf stage, placed in a plastic container vertical 21cm × horizontal 13cm × depth 3 cm, the common cutworm (Spodoptera litura) 3 larvae therein 10 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 the following table.

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 kidney beans cut into 5cm x 2.5cm was placed on moist filter paper, and 10 adult females of 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 investigated 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 the following table.

  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 (9)

The following formula (I),

(I)
A trifluoromethylsulfonylamidine derivative represented by:
(Where
A and B are same with or may be different, a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ halo alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ haloalkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ haloalkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ ~ C _{3 represents a} haloalkylsulfonyl group, a nitro group, or a cyano group,
m and n represent any integer of 1 to 5,
However, when there are a plurality of A or B, they may be the same or different. )   The amidine derivative according to claim 1, wherein A is a halogen atom. Wherein B is amidine derivative according to claim 1 is a C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group or a halogen atom. Formula (II)

(II)
(In the formula, A represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ haloalkoxy group, or a C ₁ -C ₃ alkylthio group, C ₁ -C ₃ haloalkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ haloalkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₃ haloalkylsulfonyl group, a nitro A group or a cyano group, m represents an arbitrary integer of 1 to 5, and when a plurality of A's are present, they may be the same or different.)
A compound represented by
Formula (III)

(III)
(Wherein, B is a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ haloalkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ haloalkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₃ haloalkylsulfonyl group, a nitro A group or a cyano group, n represents an arbitrary integer of 1 to 5, and 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)

(IV)
(Where
A and B are same with or may be different, a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ halo alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ haloalkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ haloalkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ ~ C _{3 represents a} haloalkylsulfonyl group, a nitro group, or a cyano group,
m and n represent any integer of 1 to 5,
When a plurality of A or B are present, they may be the same or different. )
A compound represented by
The following formula (V),

(V)
(X represents a leaving group.)
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. The following formula (VI),

(VI)
(Where
A and B are same with or may be different, a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ halo alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ haloalkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ haloalkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ ~ C _{3 represents a} haloalkylsulfonyl group, a nitro group, or a cyano group,
m and n represent any integer of 1 to 5,
When a plurality of A or B are present, they may be the same or different. )
A compound represented by
Formula (VII)

(VII)
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.   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.