TWI687161B - Ester compounds and use thereof - Google Patents

Abstract

Provide a compound with excellent pest control effect.

An ester compound and a pest control agent and pest control method using the ester compound are represented by the following general formula [Chem 1] (I):

[Where R ¹ represents a hydrogen atom or a methyl group, when R ¹ represents a methyl group, R ² also represents a methyl group, and when R ¹ represents a hydrogen atom, R ² represents the following general formula [Chem 2] (2)

(Here X and Y are the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, a C 1-4 alkyl group, a C 2-5 alkoxycarbonyl group or a C 1-4 haloalkyl group ), R ³ represents a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl].

Description

Ester compounds and their uses

The present invention relates to an ester compound, a pest control agent using the ester compound, and a pest control method.

Conventionally, various compounds have been synthesized to prevent harmful organisms (see Non-Patent Documents 1 and 2). Furthermore, Patent Documents 1, 2 and 3 disclose certain ester compounds. However, the effectiveness of the disclosed pest control ingredients may not be satisfactory.

[Patent Document 1]: Japanese Patent Laid-Open No. 57-165343

[Patent Literature 2]: Japanese Patent No. 4289331

[Patent Document 3]: Japanese Patent No. 2647411

[Non-Patent Document 1]: [Continued Development of Pharmaceuticals Volume 18 Development of Pesticides III], Guangchuan Bookstore, 1993, p.493

[Non-Patent Document 2]: [Pyrethroid (pyrethroid)], Springe, 2012

The present invention is to provide an excellent pest control effect A powerful novel ester compound and a method for eradicating pests using the ester compound are problems.

The inventors considered that the F atom on the aromatic ring of the tetrafluorobenzyl ester compound represented by transfluthrin, metofluthrin, and profluthrin Substitution of Cl atoms or Br atoms creates compounds with excellent characteristics such as improvement of residual effects. As a result of a dedicated review, it was found that the ester compound represented by the following general formula (1) (hereinafter referred to as a Cl-containing ester compound), or the ester compound represented by the following general formula (I) (hereinafter referred to as containing In the case of Br ester compound), it has an excellent pest control effect, and the present invention has been completed.

In other words, the present invention relates to the following inventions.

[1] An ester compound, represented by the following general formula [Chem 1] (1):

[Where R ¹ represents a hydrogen atom, and R ² is represented by the following general formula [Chem 2] (2) [Chem 2]

(Here X and Y are the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, a C 1-4 alkyl group, a C 2-5 alkoxy carbonyl group (alkoxy carbonyl group) or a C 2~ Haloalkyl of 4, when X represents a hydrogen atom, Y represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 2 to 5 carbon atoms, and X represents a halogen atom, a cyano group , Alkyl having 1 to 4 carbons, alkoxycarbonyl having 2 to 5 carbons or haloalkyl having 2 to 4 carbons, Y represents a halogen atom, cyano, alkyl having 1 to 4 carbons, or carbon Alkoxycarbonyl group having 2 to 5 or haloalkyl group having 2 to 4 carbons), R ³ represents a hydrogen atom, trifluoromethyl (trifluoromethyl), methyl, methoxy, methoxymethyl Radical, allyl, ethynyl or propynyl].

[2]. An ester compound represented by the following general formula [Chem. 3] (I):

[Where R ¹ represents a hydrogen atom R ² is represented by the following general formula [Chem 4] (II) [Chem 4]

(Here X and Y are the same or different and represent a hydrogen atom, a halogen atom, a cyano group, a C 1-4 alkyl group, a C 2-5 alkoxycarbonyl group or a C 2-5 haloalkyl group , X represents a hydrogen atom, Y represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 2 to 5 carbon atoms, X represents a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms When a group, an alkoxycarbonyl group having 2 to 5 carbon atoms or a haloalkyl group having 2 to 5 carbon atoms, Y represents a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 2 to 5 carbon atoms Carbonyl or haloalkyl having 2 to 5 carbon atoms), R ³ represents a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl or propyne base].

[3]. The ester compound as in [1] or [2], wherein R ³ is represented by a hydrogen atom.

[4]. The ester compound as in [1] or [2], wherein R ³ is represented by a methyl group.

[5]. The ester compound as in [1] or [2], wherein R ³ is represented by methoxymethyl.

[6]. The ester compound as in [1], wherein R ³ is represented by ethynyl.

[7]. An ester compound represented by the following chemical formula [Chemical 48] (38):

[8]. A pest control agent containing the ester compound according to any one of [1] to [7] as an active ingredient.

[9]. A method for controlling harmful organisms. The ester compound according to any one of [1] to [7] is applied to harmful organisms or habitats of harmful organisms. The method for controlling harmful organisms excludes use in humans or animals.

Since the compound of the present invention has an excellent pest control effect, it is useful as an effective ingredient of a pest control agent.

When the compound of the present invention has R ¹ representing a hydrogen atom, there are cases in which an optical isomer derived from two asymmetric carbon atoms at the 1 and 3 positions on the cyclopropane ring ), and in the case of isomers derived from the double bond at the 1′ position of the substituent present at the 3-position of the cyclopropane ring, the present invention includes each isomer having pest control activity and an arbitrary ratio of Structure mixture.

<Production method of Cl-containing ester compound>

The method for producing the compound of the present invention (Cl-containing ester compound) will be described.

The compound of the present invention is not particularly limited as long as it is a method for producing a general ester compound, but it can be produced by the method shown below, for example.

(Refer to Manufacturing Method 1)

表示的醇化合物(式中R³是表示氫原子、三氟甲基、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基)，與以下列的式[化6](4)：

By using the following formula [Chem 5] (3): [Chem 5]

The alcohol compound represented (wherein R ³ represents a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl), and the following formula [ Change 6] (4):

[Where R ¹ represents a hydrogen atom or a methyl group, when R ¹ represents a methyl group, R ² also represents a methyl group, and when R ¹ represents a hydrogen atom, R ² represents the following general formula [Chem 7] (2)

(Here X and Y are the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, a C 1-4 alkyl group, a C 2-5 alkoxycarbonyl group or a C 1-4 haloalkyl group The group represented by )] the carboxylic acid compound represented by or the reactive derivative thereof is reacted to obtain the compound of the present invention.

Examples of the reactive derivative include an acid halide of the carboxylic acid compound represented by formula (4), an acid anhydride of the carboxylic acid compound, and an ester of the carboxylic acid compound. Examples of the acid halide include acid chloride compounds, and examples of the ester include methyl ester and ethyl ester.

This reaction is usually carried out in a solvent in the presence of a condensing agent or a base.

Examples of the condensing agent include dicyclohexylcarbodiimide and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (1-ethyl-3- (3-dimethylaminopropyl)carbodiimide hydrochloride). In addition, examples of the base include organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine, and diisopropylethylamine.

Examples of the solvent include hydrocarbons such as toluene and hexane; ethers such as tetrahydrofuran; esters such as ethyl acetate; halogenated hydrocarbons such as chlorobenzene; and mixed solvents thereof. .

In this reaction, the molar ratio of the alcohol compound represented by the formula (3) to the carboxylic acid compound represented by the formula (4) or its reactive derivative can be arbitrarily set, preferably equal to or close to it proportion.

The alcohol compound represented by the formula (3) with respect to 1 mole of the condensing agent or base can generally be used in any ratio from 0.25 mole to an excess, preferably 0.5 mole to 2 mole. These condensing agents or bases are appropriately selected according to the type of carboxylic acid compound represented by formula (4) or its reactive derivative.

After the reaction, the reaction mixture can be filtered and the filtrate concentrated The compound of the present invention can be obtained by adding water to the reaction mixture or subjecting it to ordinary post-treatment operations such as organic solvent extraction and concentration. The obtained compound of the present invention can be purified by operations such as chromatography and distillation.

(Refer to Manufacturing Method 2)

也就是說，可藉由在不活性溶劑(例如己烷、甲苯、四氫呋喃、乙醚等)中，使酯化合物(5)(式中R是表示碳數1~4的烷基，R³是表示氫原子、三氟甲基、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基)與還原劑(例如鋁氫化鋰(lithium aluminum hydride)、二異丁基氫化鋁(diisobutylaluminium hydride)等)在-30~20℃反應1~10小時而製造。 The alcohol compound represented by the formula (3) in the above Reference Manufacturing Method 1 (wherein R ³ represents a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl Or propynyl) can be produced by, for example, the following synthetic pathway [Chem 8] (5) → (3):

That is, the ester compound (5) (where R is an alkyl group having 1 to 4 carbon atoms and R ³ is represented by an inactive solvent (such as hexane, toluene, tetrahydrofuran, ether, etc.) Hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl) and reducing agents (such as lithium aluminum hydride, diisobutyl Aluminum hydride (diisobutylaluminium hydride) is produced by reacting at -30~20℃ for 1~10 hours.

(Refer to Manufacturing Method 3)

也就是說，可藉由對酯化合物(6)透過Sandmeyer反應進行氯化而製造。具體上可藉由在醋酸與濃鹽酸的混合溶劑中慢慢地加入亞硝酸鈉的水溶液並在冰冷下使酯化合物(6)反應30分~1小時調製重氮鎓鹽中間物(diazonium salt intermediate)，在此處分割添加氯化銅(I)(cuprous chloride)，在20~60℃使其反應1~10小時而製造。 The ester compound represented by formula (5) in the above Reference Production Method 2 (where R is an alkyl group having 1 to 4 carbon atoms, R ³ is a hydrogen atom, trifluoromethyl, methyl, methoxy, (Methoxymethyl, allyl, ethynyl or propynyl) can be produced by, for example, the following synthetic route [Chem. 9] (6) → (5):

That is, it can be produced by chlorination of the ester compound (6) through Sandmeyer reaction. Specifically, a diazonium salt intermediate can be prepared by slowly adding an aqueous solution of sodium nitrite to a mixed solvent of acetic acid and concentrated hydrochloric acid, and reacting the ester compound (6) under ice cooling for 30 minutes to 1 hour. ), where copper chloride (I) (cuprous chloride) is added separately, and reacted at 20 to 60°C for 1 to 10 hours.

(Refer to Manufacturing Method 4)

也就是說，可藉由在有機溶劑(例如乙酸乙酯、己烷、甲苯、四氫呋喃、乙醚、碳數1~3的醇等)中在金屬觸媒(例如鈀碳、鉑、銠、釕等)存在下於氫環境下在10~30℃使酯化合物(7)反應1~10小時而製造。 The ester compound represented by the formula (6) in the above Reference Production Method 3 (where R is an alkyl group having 1 to 4 carbon atoms, R ³ is a hydrogen atom, trifluoromethyl, methyl, methoxy, (Methoxymethyl, allyl, ethynyl or propynyl) can be produced by, for example, the following synthetic route [Chem 10] (7) → (6): [Chem 10]

That is to say, it can be done by using metal catalysts (such as palladium on carbon, platinum, rhodium, ruthenium, etc.) in organic solvents (such as ethyl acetate, hexane, toluene, tetrahydrofuran, diethyl ether, alcohols with 1 to 3 carbon atoms, etc.) ) It is produced by reacting the ester compound (7) in a hydrogen environment at 10 to 30°C for 1 to 10 hours.

(Refer to Manufacturing Method 5)

也就是說，可藉由在不活性溶劑(例如己烷、甲苯、四氫呋 喃、乙醚等)中在鹼(例如三乙胺、乙基二異丙胺(ethyldiisopropylamine))存在下使酯化合物(8)與苯甲胺(benzylamine)在60~100℃反應5~15小時而製造。 The ester compound represented by the formula (7) in the above Reference Production Method 4 (where R is an alkyl group having 1 to 4 carbon atoms, R ³ is a hydrogen atom, trifluoromethyl, methyl, methoxy, (Methoxymethyl, allyl, ethynyl or propynyl) can be produced by, for example, the following synthetic route [Chem. 11] (8) → (7):

That is to say, the ester compound (8) can be combined with an inactive solvent (such as hexane, toluene, tetrahydrofuran, ether, etc.) in the presence of a base (such as triethylamine, ethyldiisopropylamine). Benzylamine (benzylamine) is produced by reacting at 60-100°C for 5-15 hours.

On the other hand, carboxylic acid compounds represented by formula (4) or reactive derivatives thereof are well-known substances.

Examples of the compound of the present invention include the following compounds.

Compound A1 of the present invention; 2-chloro-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethyl Cyclopropane carboxylate, compound B1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2 ,2-dimethylcyclopropane carboxylate, compound C1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl )-2,2-dimethylcyclopropane carboxylate, compound D1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2 -Difluoro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound E1 of the present invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3 -(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound F1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1RS) -Trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound G1 of the invention; 2-chloro-3,5,6 -Trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound H1 of the present invention; 2-chloro- 3,5,6-Trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, this Invention compound I1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans -3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound J1 of the present invention; 2-chloro-3,5,6-trifluorobenzyl ( 1R)-trans, cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound K1 of the invention; 2-chloro-3,5 ,6-trifluorobenzyl (1R)-cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound L1 of the invention; 2- Chloro-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl Cyclopropane carboxylate, compound M1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3- Trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound N1 of the present invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-cis-3- [(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound O1 of the invention; 2-chloro-3,5, 6-trifluorobenzyl (1R)-trans, cis-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers to double bonds) : Z/E=about 8/1), compound P1 of the present invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2- Dimethylcyclopropane carboxylate (ratio of isomers with respect to double bond: Z/E=about 8/1), compound Q1 of the present invention; 2-chloro-3,5,6-trifluorobenzyl (1R )-Trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound R1 of the invention; 2-chloro -3,5,6-trifluorobenzyl (1R)-trans -3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound S1 of the invention; 2-chloro-3,5,6- Trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate, the present invention Compound T1; 2-chloro-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-di Methylcyclopropane carboxylate, compound U1 of the present invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-cyano- 1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound V1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3-[( Z)-(2-cyano-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound W1 of the invention; 2-chloro-3,5,6-trifluorobenzyl 2, 2,3,3-tetramethylcyclopropane carboxylate, compound A2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3 -(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound B2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound C2 of the invention; 2-chloro-4-methyl -3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound D2 of the present invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-difluoro-1-vinyl)-2,2-di Methylcyclopropane carboxylate, compound E2 of the present invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-difluoro-1 -Vinyl)-2,2-dimethylcyclopropane carboxylate, compound F2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1RS)- Trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound G2 of the invention; 2-chloro-4-methyl-3 ,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound H2 of the present invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-di Methylcyclopropane carboxylate, compound I2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1 -Vinyl)-2,2-dimethylcyclopropane carboxylate, compound J2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis Formula-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound K2 of the present invention; 2-chloro-4-methyl-3,5,6 -Trifluorobenzyl (1R)-cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound L2 of the present invention; 2-chloro- 4-methyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2 -Dimethylcyclopropane carboxylate, compound M2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2- Chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound N2 of the invention; 2-chloro-4-methyl-3,5,6- Trifluorobenzyl (1R)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, Compound O2 of the present invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)- Trans, cis-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 8/1), the present invention Compound P2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (Regarding the ratio of double bond isomers: Z/E=about 8/1), the compound Q2 of the present invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans Formula, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound R2 of the present invention; 2-chloro-4- Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane Carboxylic acid ester, compound S2 of the present invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-methoxy (Carbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate, compound T2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)- Cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate, compound U2 of the invention; 2-chloro-4-methyl -3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-cyano-1-propenyl)]-2,2-dimethylcyclopropane Carboxylic acid ester, compound V2 of the present invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(Z)-(2-cyano-1- Propenyl)]-2,2-dimethylcyclopropane carboxylate, compound W2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl 2,2,3,3- Tetramethylcyclopropane carboxylate, Compound A3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1-propenyl) -2,2-dimethylcyclopropane carboxylate, compound B3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis -3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound C3 of the invention; 2-chloro-4-methoxymethyl-3,5,6 -Trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound D3 of the invention; 2-chloro-4- Methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-difluoro-1-vinyl)-2,2-dimethyl ring Propane carboxylate, compound E3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-difluoro-1 -Vinyl)-2,2-dimethylcyclopropane carboxylate, compound F3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans Formula, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound G3 of the present invention; 2-chloro-4-methoxymethyl -3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, Compound H3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)- 2,2-dimethylcyclopropane carboxylate, compound I3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound J3 of the invention; 2-chloro-4-methoxy Methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropanecarboxylic acid Ester, compound K3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-cis-3-(2,2-dibromo-1-vinyl )-2,2-dimethylcyclopropane carboxylate, compound L3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans, cis Formula-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound M3 of the invention; 2-chloro-4-methoxy Methyl-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2 -Dimethylcyclopropane carboxylate, compound N3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z) -2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound O3 of the present invention; 2-chloro-4-methoxymethyl- 3,5,6-trifluorobenzyl (1R)-trans, cis-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (for double bond isomers) Ratio: Z/E=about 8/1), compound P3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(1 -Propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 8/1), the compound of the present invention Q3; 2-chloro-4-methyl Oxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound R3 of the invention; 2 -Chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2 ,2-dimethylcyclopropane carboxylate, compound S3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3 -[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate, compound T3 of the invention; 2-chloro-4-methoxymethyl- 3,5,6-Trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate The compound U3 of the present invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-cyano -1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound V3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R )-Trans-3-[(Z)-(2-cyano-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound W3 of the invention; 2-chloro-4-methyl Oxymethyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate, compound A4 of the invention; 2-chloro-4-ethynyl-3,5, 6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound B4 of the invention; 2- Chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane Carboxyl Acid ester, compound C4 of the present invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2, 2-Dimethylcyclopropane carboxylate, compound D4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2, 2-difluoro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound E4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R )-Trans-3-(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound F4 of the invention; 2-chloro-4-ethynyl-3, 5,6-trifluorobenzyl (1RS)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compounds of the invention G4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethyl Cyclopropane carboxylate, compound H4 of the present invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro -1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound I4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans -3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound J4 of the present invention; 2-chloro-4-ethynyl-3,5,6- Trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound K4 of the invention; 2- Chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound L4 of the invention; 2-chloro-4-ethynyl- 3,5,6-Trifluorobenzyl (1RS)-trans, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl ring Propane carboxylate, compound M4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3 ,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound N4 of the present invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl ( 1R)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound O4 of the present invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (Regarding the ratio of double bond isomers: Z/E=about 8/1), the compound P4 of the present invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans Formula-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 8/1), compound Q4 of the present invention; 2 -Chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2 ,2-dimethylcyclopropane carboxylate, compound R4 of the present invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)- (2-Methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound S4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl base (1R)-trans, cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate, compound T4 of the invention; 2 -Chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2- Dimethylcyclopropane carboxylate, compound U4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)- (2-cyano-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound V4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(Z)-(2-cyano-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound W4 of the invention; 2-chloro-4 -Ethynyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate, compound A5 of the invention; 2-chloro-3,5,6-trifluoro-4 -Trifluoromethylbenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound B5 of the present invention; 4- Allyl-2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (about double bond Ratio of isomers: Z/E=about 8/1), compound C5 of the present invention; 2-chloro-4-propynyl-3,5,6-trifluorobenzyl (1R)-trans-3 -(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound D5 of the invention; 2-chloro-4-methoxy-3,5,6-tri Fluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate.

<Manufacturing method of Br-containing ester compound>

The method for producing the compound of the present invention (Br-containing ester compound) will be described.

The compound of the present invention is not particularly limited as long as it is a method for producing a general ester compound, but it can be produced by the method shown below, for example.

(Refer to Manufacturing Method 1)

表示的醇化合物(式中R³是表示氫原子、三氟甲基、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基)，與以下列的式[化13](IV)：

By using the following formula [Chem 12] (III):

The alcohol compound represented (wherein R ³ represents a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl), and the following formula [ Change 13] (IV):

[Where R ¹ represents a hydrogen atom or a methyl group, when R ¹ represents a methyl group, R ² also represents a methyl group, and when R ¹ represents a hydrogen atom, R ² represents the following general formula ]

(Here X and Y are the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, a C 1-4 alkyl group, a C 2-5 alkoxycarbonyl group or a C 1-5 haloalkyl group The group represented by )] the carboxylic acid compound represented by or the reactive derivative thereof is reacted to obtain the compound of the present invention.

Examples of the reactive derivative include an acid halide of the carboxylic acid compound represented by formula (IV), an acid anhydride of the carboxylic acid compound, and an ester of the carboxylic acid compound. Examples of the acid halide include acid chloride compounds, and examples of the ester include methyl ester and ethyl ester.

This reaction is usually carried out in a solvent in the presence of a condensing agent or a base.

Examples of the condensing agent include dicyclohexylcarbodiimide and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. In addition, examples of the base include organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine, and diisopropylethylamine.

Examples of the solvent include hydrocarbons such as toluene and hexane; ethers such as tetrahydrofuran; esters such as ethyl acetate; halogenated hydrocarbons such as chlorobenzene; and mixed solvents thereof.

In this reaction, the molar ratio of the alcohol compound represented by the formula (III) to the carboxylic acid compound represented by the formula (IV) or its reactive derivative can be arbitrarily set, preferably equal to or close to it proportion.

The alcohol compound represented by the general formula (III) per 1 mole of the condensing agent or base can generally be used in any ratio from 0.25 mole to an excess, preferably 0.5 mole to 2 mole. These condensing agents or bases are based on the carboxyl groups represented by the general formula (IV) The kind of acid compound or its reactive derivative is appropriately selected.

The reaction mixture after completion of the reaction can be obtained by filtering it and concentrating the filtrate, or by adding water to the reaction mixture and then subjecting it to usual post-treatment operations such as organic solvent extraction and concentration. The obtained compound of the present invention can be purified by operations such as chromatography and distillation.

(Refer to Manufacturing Method 2)

也就是說，可藉由在不活性溶劑(例如己烷、甲苯、四氫呋喃、乙醚等)中，使以通式(VI)表示的酯化合物(式中R是表示碳數1~4的烷基，R³是表示氫原子、三氟甲基、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基)與還原劑(例如鋁氫化鋰、二異丁基氫化鋁等)在-30~20℃反應1~10小時而製造。 The alcohol compound represented by the general formula (III) in the above Reference Manufacturing Method 1 (wherein R ³ represents a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, acetylene Group or propynyl group) can be produced by, for example, the following synthetic route [Chem. 15] (VI) → (III):

That is, the ester compound represented by the general formula (VI) (where R is an alkyl group having 1 to 4 carbon atoms) can be used in an inactive solvent (such as hexane, toluene, tetrahydrofuran, ether, etc.) , R ³ represents a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl) and a reducing agent (such as lithium aluminum hydride, diisobutyl Aluminum hydride, etc.) -30 ~ 20 ℃ reaction for 1 to 10 hours to produce.

(Refer to Manufacturing Method 3)

也就是說，可藉由對以通式(VII)表示的酯化合物(式中R是表示碳數1~4的烷基，R³是表示氫原子、三氟甲基、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基)透過Sandmeyer反應進行溴化而製造。具體上可藉由在室溫下將溴化四丁銨(tetrabutylammonium bromide)、樟腦磺酸(camphorsulfonic acid)、亞硝酸鈉、二價溴化銅依次添加到以通式(VII)表示的酯化合物(式中R是表示碳數1~4的烷基，R³是表示氫原子、三氟甲基、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基)的乙腈(acetonitrile)溶液，在20~60℃使其反應1~48小時而製造。 The ester compound represented by the general formula (VI) in the above Reference Manufacturing Method 2 (where R is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom, trifluoromethyl, methyl, methoxy , Methoxymethyl, allyl, ethynyl or propynyl) can be produced by, for example, the following synthetic route [Chem. 16](VII)→(VI):

That is, the ester compound represented by the general formula (VII) (where R is an alkyl group having 1 to 4 carbon atoms and R ³ is a hydrogen atom, trifluoromethyl group, methyl group, and methoxy group) Group, methoxymethyl group, allyl group, ethynyl group or propynyl group) is produced by bromination by Sandmeyer reaction. Specifically, tetrabutylammonium bromide, camphorsulfonic acid, sodium nitrite, and divalent copper bromide can be sequentially added to the ester compound represented by the general formula (VII) at room temperature (Where R is an alkyl group having 1 to 4 carbon atoms, R ³ is a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl ) Acetonitrile (acetonitrile) solution, at 20 ~ 60 ℃ for 1 ~ 48 hours to produce.

(Refer to Manufacturing Method 4)

也就是說，可藉由在有機溶劑(例如乙酸乙酯、己烷、甲苯、四氫呋喃、乙醚、碳數1~3的醇等)中在金屬觸媒(例如鈀碳、鉑、銠、釕等)存在下於氫環境下在10~30℃使以通式(VIII)表示的酯化合物(式中R是表示碳數1~4的烷基，R³是表示氫原子、三氟甲基、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基)反應1~10小時而製造。 The ester compound represented by the general formula (VII) in the above Reference Manufacturing Method 3 (where R is an alkyl group having 1 to 4 carbon atoms, R ³ is a hydrogen atom, trifluoromethyl, methyl, methoxy , Methoxymethyl, allyl, ethynyl or propynyl) can be produced by, for example, the following synthetic route [Chem. 17] (VIII) → (VII):

That is to say, it can be done by using metal catalysts (such as palladium on carbon, platinum, rhodium, ruthenium, etc.) in organic solvents (such as ethyl acetate, hexane, toluene, tetrahydrofuran, diethyl ether, alcohols with 1 to 3 carbon atoms, etc.) ) An ester compound represented by the general formula (VIII) (where R is an alkyl group having 1 to 4 carbon atoms, R ³ is a hydrogen atom, trifluoromethyl, Methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl) reacted for 1 to 10 hours to produce.

(Refer to Manufacturing Method 5)

也就是說，可藉由在不活性溶劑(例如己烷、甲苯、四氫呋喃、乙醚等)中在鹼(例如三乙胺、乙基二異丙胺)存在下使以通式(IX)表示的酯化合物(式中R是表示碳數1~4的烷基，R³是表示氫原子、三氟甲基、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基)與苯甲胺在60~100℃反應5~15小時而製造。 The ester compound represented by the general formula (VIII) in the above Reference Manufacturing Method 4 (where R is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom, trifluoromethyl, methyl, methoxy , Methoxymethyl, allyl, ethynyl or propynyl) can be produced by, for example, the following synthetic route [Chem 18] (IX) → (VIII): [Chem 18]

That is, the ester represented by the general formula (IX) can be used in the presence of a base (eg, triethylamine, ethyldiisopropylamine) in an inactive solvent (eg, hexane, toluene, tetrahydrofuran, diethyl ether, etc.) Compound (where R is an alkyl group having 1 to 4 carbon atoms, R ³ is a hydrogen atom, trifluoromethyl, methyl, methoxy, methoxymethyl, allyl, ethynyl or propyne Base) and benzylamine reacted at 60~100℃ for 5~15 hours.

On the other hand, carboxylic acid compounds represented by the general formula (IV) or reactive derivatives thereof are well-known substances.

Examples of the compound of the present invention include the following compounds.

Compound 1 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethyl Cyclopropane carboxylate, compound 2 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2 ,2-dimethylcyclopropane carboxylate, compound 3 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl )-2,2-dimethylcyclopropane carboxylate, compound 4 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2 -Difluoro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, Compound 5 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-difluoro-1-vinyl)-2,2-dimethyl ring Propane carboxylate, compound 6 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2,2-dichloro-1-vinyl)- 2,2-dimethylcyclopropane carboxylate, compound 7 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1 -Vinyl)-2,2-dimethylcyclopropane carboxylate, compound 8 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-( 2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 9 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans Formula-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 10 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 11 of the present invention; 2-bromo-3, 5,6-trifluorobenzyl (1R)-cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 12 of the present invention; 2 -Bromo-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-di Methylcyclopropane carboxylate, compound 13 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3 -Trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound 14 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-cis-3 -[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound 15 of the present invention; 2-bromo-3,5 ,6-trifluorobenzyl (1R)-trans, cis Formula-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomer with respect to double bond: Z/E=about 8/1), the compound of the present invention 16; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate Structure ratio: Z/E = about 8/1), compound 17 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E) -(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound 18 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R) -Trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound 19 of the present invention; 2-bromo-3,5 ,6-Trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate The compound 20 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2, 2-dimethylcyclopropane carboxylate, compound 21 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-cyano-1- Propenyl)-2,2-dimethylcyclopropane carboxylate (ratio of isomers with respect to double bond: Z/E=about 2/1), the compound 22 of the present invention; 2-bromo-3,5, 6-trifluorobenzyl (1R)-trans-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 2/1), compound 23 of the present invention; 2-bromo-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylic acid ester, compound 24 of the present invention ; 2-Bromo-4-methyl-3,5,6-trifluorobenzyl (1RS)- Trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound 25 of the present invention; 2-bromo-4-methyl-3,5 ,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound 26 of the present invention; 2 -Bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid Ester, compound 27 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-difluoro-1-vinyl )-2,2-dimethylcyclopropane carboxylate, compound 28 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2 ,2-difluoro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 29 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl ( 1RS)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 30 of the present invention; 2-bromo-4-methyl -3,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, the present invention Compound 31; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2, 2-dimethylcyclopropane carboxylate, compound 32 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-di (Chloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 33 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans Formula, cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 34 of the present invention; 2-bromo-4-methyl-3, 5,6-trifluorobenzyl (1R)- Cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 35 of the present invention; 2-bromo-4-methyl-3,5, 6-trifluorobenzyl (1RS)-trans, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropane carboxylate 3. Compound 36 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-tri Fluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound 37 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-cis Formula-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound 38 of the present invention; 2-bromo- 4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (about double bond Ratio of isomers: Z/E = about 8/1), compound 39 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3- (1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 8/1), the present compound 40; 2-bromo-4 -Methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-di Methylcyclopropane carboxylate, compound 41 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methyl Oxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound 42 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R) -Trans, cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane Alkyl carboxylate, compound 43 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl- 1-vinyl)]-2,2-dimethylcyclopropane carboxylate, compound 44 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans , Cis-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 2/1) 2. Compound 45 of the present invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-cyano-1-propenyl)-2,2- Dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 2/1), the present compound 46; 2-bromo-4-methyl-3,5,6-tri Fluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate, compound 47 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS) -Trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound 48 of the present invention; 2-bromo-4-methoxymethyl -3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, the present invention Compound 49; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2- Dimethylcyclopropane carboxylate, compound 50 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2 ,2-difluoro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 51 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluoro Benzyl (1R)-trans-3-(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 52 of the present invention; 2-bromo-4-methoxy Methyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylic acid Ester, compound 53 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl )-2,2-dimethylcyclopropane carboxylate, compound 54 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis Formula-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 55 of the present invention; 2-bromo-4-methoxymethyl-3, 5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 56 of the present invention; 2 -Bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl)-2,2 -Dimethylcyclopropane carboxylate, compound 57 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-cis-3-(2,2 -Dibromo-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 58 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropane carboxylate, compound 59 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound 60 of the present invention ; 2-Bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro- 1-propenyl]-2,2-dimethylcyclopropane carboxylate, compound 61 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)- Trans, cis-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 8/1), the present invention Compound 62; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane Carboxylic acid ester (ratio of isomers with respect to double bond: Z/E = about 8/1), compound 63 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate, compound 64 of the present invention; 2-Bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]- 2,2-dimethylcyclopropane carboxylate, compound 65 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis- 3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate, compound 66 of the invention; 2-bromo-4-methoxymethyl -3,5,6-Trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylic acid Ester, compound 67 of the present invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E = About 2/1), compound 68 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-cyano-1 -Propenyl)-2,2-dimethylcyclopropane carboxylate (ratio of isomers with respect to double bond: Z/E=about 2/1), compound 69 of the present invention; 2-bromo-4-methyl Oxymethyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate, compound 70 of the present invention; 2-bromo-3,5,6-trifluoro- 4-trifluoromethylbenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 71 of the present invention; 4 -Allyl-2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethyl ring Propane carboxylate, compound 72 of the present invention; 4-allyl-2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2- Dimethylcyclopropane carboxylate (the ratio of isomers with respect to double bonds: Z/E=about 8/1), the present compound 73; 2-bromo-4-propynyl-3,5,6- Trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate, compound 74 of the present invention; 2-bromo-4 -Methoxy-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate,

<Formulation of Cl-containing ester compound and Br-containing ester compound>

The pest control agent of the present invention can also be used alone as the compound of the present invention (Cl-containing ester compound, Br-containing ester compound) itself, but can also be used as The following preparations are used. Examples of such preparations include mosquito coils, mosquito coils or mosquito coil-like liquid heating evapotranspiration agents, fan-type mosquito coils, oils, emulsions, aerosols, carbon dioxide gas preparations, wettable powders (wettable powder), Flowable agent (suspending agent in water, emulsifying agent in water, etc.), microcapsules, powder, granules, lozenges, piezo type insecticides, heating smoker (self-ignition smoker) Agent, chemical reaction type smoke agent, porous ceramic board smoke agent, etc.), non-heated evapotranspiration agent (resin evaporator, paper evaporator, nonwoven evaporator, woven evaporator, sublimation lozenge, etc.), aerosol ( Fogging agent, direct contact agent (sheet contact agent, tape contact agent, mesh contact agent, etc.), ULV agent and poison bait.

Examples of the method of formulation include the following methods.

[1]. A method of mixing the compound of the present invention with a solid carrier, liquid carrier, gaseous carrier, bait, etc. as needed, and adding and processing a surfactant and other auxiliary agents for formulation.

[2]. A method of impregnating a base material that does not contain an active ingredient with the compound of the present invention.

[3]. A method of forming after mixing the compound of the present invention and a substrate.

These preparations also depend on the form of the preparation, and usually contain 0.001 to 98% of the compound of the present invention in a weight ratio.

Examples of solid carriers used in the formulation include clays (kaolin clay, diatomaceous earth, bentonite, fubasami clay, acid clay) ) Etc.); synthetic hydrous silica; talc; ceramic; its Fine powders and granules of his inorganic minerals (sericite, activated carbon, calcium carbonate, silica, etc.); solid materials at room temperature (2,4,6-triisopropyl- 1,3,5-trioxane (2,4,6-triisopropyl-1,3,5-trioxane), naphthalene, p-dichlorobenzene, camphor, adamantine, etc. ) And felts consisting of one or more of the following: wool, silk, cotton, hemp, pulp, synthetic resins (eg low density polyethylene, linear low density polyethylene, high density) Polyethylene-based resins such as polyethylene; ethylene-vinyl ester copolymers such as ethylene vinyl acetate copolymer; ethylene-methyl methacrylate copolymers (ethylene-vinyl ester copolymer) Ethylene methacrylic acid copolymer such as methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, etc.; ethylene-methyl acrylate copolymer acrylate copolymer, ethylene-ethyl acrylate copolymer, etc. ethylene-acrylate copolymer (ethylene acrylate copolymer); ethylene-acrylic acid copolymer (ethylene-acrylic acid copolymer), etc. Carboxylic acid copolymers (ethylene-vinyl carboxylic acid copolymer); polypropylene resins such as polypropylene and propylene-ethylene copolymers; poly-4-methylpentene-1 (poly-4-methylpentene-1 -1), polybutene-1, polybutadiene, polystyrene, acrylonitrile-styrene resin; acrylonitrile-butadiene- Styrene resin (acrylonitrile-butadiene-styrene resin), styrene-conjugated diene block copolymer, styrene-conjugated diene block copolymer hydrogenated products such as styrene-based elastomer (elastomer); fluoro resin; acrylic resins such as polymethyl methacrylate; polyamide resins such as nylon 6 and nylon 66 ; Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycarbonate (polycarbonate), polyacetal, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polybenzene Porous resins such as polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, foamed polyurethane, foamed polypropylene, foamed ethylene, etc.), glass, metal, ceramics, etc. Fiber; Cloth; Knitted fabric; Sheet; Paper; Yarn; Foam; Porous body and multifilament.

Examples of the liquid carrier include aromatic or aliphatic hydrocarbons (xylene, alkylnaphthalene, phenyl xylyl ethane, kerosene, light oil, hexane, Cyclohexane, etc.); alcohols (methanol, ethanol, isopropanol, butanol, hexanol, benzyl alcohol, ethylene glycol, etc.); ethers (diethyl ether, ethylene glycol dimethyl ether) , Diethylene glycol monoethyl ether monoethyl ether), diethylene glycol monobutyl ether, propylene glycol monomethyl ether, tetrahydrofuran, etc.); esters (ethyl acetate, butyl acetate, etc.); ketones (acetone , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.); nitriles (acetonitrile, isobutyronitrile, etc.); sulfoxides (dimethyl sulfoxide) (Dimethyl sulfoxide), etc.; acid amides (N,N-dimethylformamide), N-methyl-pyrrolidone, etc. ), alkylidene carbonates (propylene carbonate, etc.); vegetable oils (soybean oil, cottonseed oil, etc.); vegetable essential oils (orange oil, hyssopoid oil) (hyssop oil), lemon oil (lemon oil), etc.) and water.

Examples of the gaseous carrier include compressed gas such as butane gas, chlorofluorocarbon gas, liquefied petroleum gas (LPG (Liquefied Petroleum Gas), dimethyl ether, and carbonic acid gas).

Examples of the surfactant include alkyl sulfate ester salts, alkyl sulfonate salts, alkyl aryl sulfonate salts, alkyl aryl ethers, polyoxyethylene compounds of alkyl aryl ethers, and polyethylene glycol. Glycol ethers, polyol esters and sugar alcohol derivatives.

Examples of other auxiliary agents for formulations include fixatives, dispersants, stabilizers, and the like, and specific examples include casein, gelatin, and polysaccharides (starch, gum arabic). , Cellulose derivatives, alginic acid, etc.), lignin derivatives, bulking Earth, sugars, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone), polyacrylic acid, etc., BHT (2,6-di-tertiary butyl-4-cresol ( 2,6-di-tert-butyl-4-methylphenol) and BHA (2-tert-butyl-4-methoxyphenol) and 3-tert-butyl-4-methoxyphenol A mixture of methoxyphenol). It may be appropriate to mix colorants, fragrances, etc. as needed.

Examples of the base material for mosquito coils include plant powders such as wood powder and pyrethrum extract powder, and binders such as red powder, starch, carboxymethyl cellulose and gluten. (bonding agent).

Examples of the base material of the mosquito coil sheet include those in which cotton linters are coagulated into plates, and those in which fibrils of a mixture of cotton linters and pulp are coagulated into plates.

Examples of the base material of the self-ignition type smoke agent include: nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose, wood powder, and other combustion exothermic agents; Thermal decomposition stimulants for alkali metal salts and alkaline earth metal salts; oxygen carriers such as potassium nitrate; combustion aids such as melamine and wheat starch; extenders such as diatomaceous earth and synthetic pastes Binding agent.

Examples of the base material of the chemical reaction type smoke agent include: heat generating agents such as alkali metal sulfides, polysulfides, hydrosulfides, and calcium oxide; and catalysts such as iron carbide and activated clay ( catalyzer); azodicarbonamide, azodicarbonamide (benzenesulfonyl hydrazide), dinitropentamethylenetetramine (dinitropentamethylenetetramine), polystyrene, polyurethane and other organic blowing agents and natural fiber sheets, synthetic fiber sheets and other fillers.

Examples of resins used as base materials for resin evaporating agents include polyethylene resins such as low-density polyethylene, linear low-density polyethylene, and high-density polyethylene; and ethylene-vinyl acetate copolymers and other ethylene-based resins. Vinyl ester copolymer; ethylene-methyl acrylate copolymer such as ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer; ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer Ethylene-acrylic acid ester copolymer; ethylene-vinyl carboxylic acid copolymer such as ethylene-acrylic acid copolymer; polypropylene-based resins such as polypropylene and propylene-ethylene copolymer; poly-4-methylpentene-1 , Polybutene-1, polybutadiene, polystyrene, acrylonitrile-styrene resin; acrylonitrile-butadiene-styrene resin, styrene-conjugated diene block copolymer, styrene-copolymer Styrene-based elastomers such as hydrogenated products of conjugated diene block copolymers; fluororesins; acrylic resins such as polymethyl methacrylate; polyamide-based resins such as nylon 6 and nylon 66; polyethylene terephthalate Polyester resins such as diesters, polyethylene naphthalate, and polybutylene terephthalate; polycarbonate, polyacetal, polyarylate, hydroxybenzoic acid polyester, polyetheramide , Polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, etc., these substrates can be used alone or in a mixture of two or more, or can be added to these substrates as needed Phthalate esters (dimethyl phthalate, dioctyl phthalate, etc.), adipic acid esters, stearic acid, etc. Plasticizer. Resin evaporating agent can be prepared by mixing the compound of the present invention After training in the above-mentioned base material, it is obtained by injection molding, extrusion molding, press molding and the like. The obtained resin preparation may be further processed into a shape such as a plate shape, a film shape, a tape shape, a mesh shape, a rope shape, and the like through further procedures such as molding and cutting. Such resin preparations can be processed as non-heating evapotranspiration agents, animal collars, animal ear tags, sheet preparations, attractive tapes, attractive ropes, horticultural pillars, and long-lasting insecticide nets, for example.

Examples of the base material for poison bait include: bait components such as grain flour, vegetable oil, sugar, and crystalline cellulose; antioxidants such as BHT, nordihydroguaiaretic acid; and dehydroacetic acid Preservatives such as chili powder; ingestion preventives to prevent children or pets from eating by mistake; pest-attractive spices such as cheese spices, onion spices, peanut oil, etc.

The compound of the present invention can also be used in combination or in combination with other insecticides, acaricides, fungicides, herbicides, repellents, synergists, fertilizers, and soil improvement materials.

Examples of the active ingredients of such insecticides and acaricides include:

[1], pyrethroid (pyrethroid) compounds

Pyrethrin, allethrin, prallethrin, furamethrin, resmethrin, phthalthrin, tetramethrin ), imiprothrin, empenthrin, transfluthrin, metofluthrin, profluthrin (profluthrin), phenothrin, cyphenothrin, permethrin, cypermethrin, cyfluthrin, beta-cyfluthrin , Fenpropathrin, bifenthrin, cycloprothrin, deltamethrin, flumethrin, anacrinathrin, tralomethrin, sairin Cyhalothrin, lambda-cyhalothrin, tefluthrin, fenvalerate, fluvalinate, etofenprox, silafluofen ), momfluorothrin, dimefluthrin, etc.;

[2], organic phosphorus compounds

Acetate, butathiofos, diazinon, dichlorvos (DDVP), dimethoate, dimethoate, fenthion (MPP), promethone (fenitrothion: MEP), marathon (malathion), bifenson (pyridaphenthion), plus pine (propaphos), triclosan (triclorfon: DEP), etc.;

[3], carbamate (carbamate) compounds

Carbaryl, carbofuran, fenobucarb, isoprocarb (MIP), metomyl, NAC, propoxur (PHC), etc.;

[4]. Nereis toxin compounds

Cartap, bensultap, etc.;

[5], neonicotinoid compounds

Imidacloprid, nitenpyram, miclopyr (acetamiprid), thiamethoxam, thiacloprid, dinotefuran, clothianidin, etc.;

[6], benzoylurea (benzoylurea) compounds

Chlorfluazuron, bistrifluron, diflubenzuron, flufenoxuron, hexaflumuron, teflubenzuron, triflumuron Wait;

[7], phenylpyrazole (phenylpyrazole) compounds

Fipronil, pyriprole, pyrafluprole, etc.;

[8], hydrazine compounds

Chromafenozide, halofenozide, methoxyfenozide, etc.;

[9] Natural pesticides

Machine oil, nicotine sulfate;

[10], Other pesticides

Avermectin-B, buprofezin, chlorphenapyr, hydroprene, metoprene, indoxacarb, evil insects Ketone (metoxadiazone), milbemycin-A (milbemycin-A), pyridalyl (pyridalyl), pyriproxyfen (pyriproxyfen), spinosad (spinosad), sulfluramid (sulfluramid), desfenrex tolfenpyrad), flubendiamide, cyflumetofen, methyl bromide, potassium oleate, etc.

Examples of effective ingredients of the repellent include N,N-diethyl-m-toluamide, limonene, linalool, and citronellal. (citronellal), menthol (menthol), menthone (menthone), hinokitiol (hinokitiol), geraniol (geraniol), p-menthane-3,8-diol (p-menthane-3,8-diol) , Eucalyptol, carane-3,4-diol, icaridin, IR-3535, MGK-R-326, MGK-R- 874 etc.

As an active ingredient of a synergist, for example, 5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxazole (5- [2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxole), N-(2-ethylhexyl) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-en-2,3-dicarboximide, octachlorodipropyl ether, isobornyl thiocyanoacetate, N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo[2.2.2]oct-5-ene-2,3-dicarboxyamide (N-(2-ethylhexyl)- 1-isopropyl-4-methylbicyclo[2.2.2]oct-5-en-2,3-dicarboximide), etc.

Examples of the harmful organisms to which the compounds of the present invention are effective include harmful insects and harmful mites such as harmful insects and mites. Specifically, the following may be mentioned.

Diptera pests: house mosquitoes such as Culex pipiens pallens, house mosquitoes, house mosquitoes, and house mosquitoes; spotted mosquitoes such as Egyptian spotted mosquitoes, white line mosquitoes; Malaria mosquitoes; rocking mosquitoes; houseflies such as house flies, livestock-rotting flies, yellow-bellied toilet flies, etc.; blowflies; meat flies; seed flies, onion flies, etc. Flower flies, fruit flies, latent flies, vinegar flies, butterfly flies, flea flies, gadfly, black mosquitoes, sting flies, midges, etc. Reticera pests: German cockroaches, smoke Cockroaches, American cockroaches, brown cockroaches, oriental cockroaches, etc.; Hymenoptera pests: leaf wasps such as ants, hornets, ant-shaped bees, cabbage leaf bees, etc.; Cryptozoan pests: dog fleas, cat fleas, humans Fleas, etc.; Licea pests: human lice, pubic lice, head lice, body lice, etc.; Isoptera pests: termites, domestic termites, etc.; Hemiptera pests: planthoppers, brown planthoppers, etc.; Leafhoppers such as black-tailed leafhoppers; aphids such as cotton aphids; stink bugs; bed bugs such as bed bugs; lepidopteran pests: borer moths such as stem borer moths and borer borers; Spodoptera litura, Burglar moths such as Spodoptera exigua, Brassica oleracea, etc.; Codling moths, leaf leaf moths, yellow poisonous moths; diamondback moths, rice nymphs, cloth moths, bag moths, etc.; Coleoptera pests: Bombycidae, Ji Weevils such as Bombycidae, rice weevils, adzuki weevils, rhododendrons such as rhubarb mealworms, and rice robberies; fanworms; mealworms, etc.; mites: American room House dust mites such as dust mites and European house dust mites; powder mites such as carrion mite mite and white spot mite; sweet mites such as sweet mites, domestic sweet mites and dust mites; carnivorous mites (Cheyletus) carnivorous mites such as malaccensis) and malacca mites (cheyletus malaccensis oudemans); fine mites; grasshopper mites; simple snail beetles; hard ticks such as Haematopsus longicornis; northern fowl mites and chicken skin mites Chicken skin mites.

The pest control method of the present invention is carried out by applying an effective amount of the compound of the present invention to a pest or a habitat of a pest in the form of the pest control agent of the present invention.

Examples of the method for applying the pest control agent of the present invention include the following methods, which can be appropriately selected according to the form and use place of the pest control agent of the present invention.

[1]. A method for treating the pest control agent of the present invention intact in a pest or pest habitat.

[2] A method for dispersing the pest control agent of the present invention in a pest or a habitat of the pest after diluting the pest control agent of the present invention with a solvent such as water.

In this case, the pest control agent of the present invention which is formulated into an emulsion, wettable powder, flowing agent, microcapsule preparation, etc. is usually diluted so that the concentration of the compound of the present invention becomes 0.1 to 10000 ppm.

[3] A method of dispersing the effective ingredient of the pest control agent of the present invention by means such as heating in the habitat of pests.

In this case, the application amount and application concentration of the compound of the present invention can be appropriately determined according to the form, application period, application site, application method, type of pest, and damage status of the pest control agent of the present invention.

When the compound of the present invention is used as a pest control application, the amount of the compound of the present invention is usually 0.001 to 100 mg/m ³ when it is applied to a space, and 0.001 to 100 mg/m ² when it is applied to a flat surface. Mosquito-repellent incense, mosquito-repellent incense tablets, etc. are applied according to the form of the preparation by heating to evaporate the active ingredient. Resin evaporating agents, paper evaporating agents, non-woven evaporating agents, woven fabric evaporating agents, sublimable lozenges, etc. can be used by being placed intact, for example, in the space of application, and placed in the preparation under air supply.

Examples of the space in which the pest control composition of the present invention is applied for pest control include: living room, dining room, bedroom, closet, closet, Japanese wardrobe, cupboard, toilet, bathhouse, In warehouses, warehouses, cars, etc., it can also be used in open spaces in the wild.

When the pest control composition of the present invention is used for domestic parasites such as cattle, horses, pigs, sheep, goats, chickens, and other small animals such as dogs, cats, rats, and mice, it can be controlled by veterinary medicine. The well-known methods above are used for animals. As a specific method of use, for the purpose of systemic control, for example, by lozenge, feed mix, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), in In the case of non-systemic control, for example, by pour-on treatment or spot-on treatment of spray oil or aqueous liquid, the hair preparation is cleaned Animals or the method of using resin evapotranspiration agent as a collar or ear tag and installing it on animals. When administered to an animal, the amount of the compound of the present invention is usually in the range of 0.01 to 100 mg relative to 1 kg of the animal's body weight.

[Example]

Hereinafter, the present invention will be described in more detail through production examples, preparation examples, effect test examples, etc., but the present invention is not limited to these examples.

<Example of Cl-containing ester compound>

A production example of the compound of the present invention (Cl-containing ester compound) is shown.

Production Example 1: Production of Compound (9)

Diisobutylaluminum hydride (1.5M toluene solution, 2.4mL, 3.60mmol) was added dropwise to toluene of methyl 2-chloro-3,5,6-trifluorobenzoate (316mg, 1.41mmol) under ice cooling (5mL) and a mixture of tetrahydrofuran (5mL). After stirring under ice cooling for 2 hours, the reaction solution was poured into 1N hydrochloric acid aqueous solution and water, and extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to silica gel column chromatography (silica gel column chromatography) to obtain 2-chloride represented by the following formula [Chem 19](9) -3,5,6-Trifluorobenzyl alcohol 266mg:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.04 (t, 1H), 4.88 (dd, 2H), 7.03 (m, 1H)

Production Example 2: Production of Compound (10)

Triethylamine (1.9mL, 13.65mmol) and benzylamine (1.00g, 9.33mmol) were added dropwise to methyl 4-methyl-2,3,5,6-tetrafluorobenzoate at room temperature (1.01 g, 4.55 mmol) in toluene (15 mL). After stirring at 100°C for 10 hours, water was added to the reaction liquid, and extraction was performed with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-benzylamino-4 represented by the following formula [Chem 20](10) -Methyl-3,5,6-trifluorobenzoate 1.18g:

Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.21 (m, 3H), 3.88 (s, 3H), 4.50 (m, 2H), 6.96 (brs, 1H), 7.29 (m, 5H)

Production Example 3: Production of Compound (11)

Palladium-carbon (117 mg) was added to methyl 2-benzylamino-4-methyl-3,5,6-trifluorobenzoate (1.15 g, 3.72 mmol) of ethyl acetate at room temperature ( 50mL) solution, replacing the reaction solution in a hydrogen environment. After stirring at room temperature for 3 hours under a hydrogen atmosphere, the reaction solution was filtered through diatomaceous earth, concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain the following formula [Chem. 21]( 11) 690 mg of methyl 2-amino-4-methyl-3,5,6-trifluorobenzoate represented by: [Chem 21]

Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.24 (m, 3H), 3.92 (s, 3H), 5.55 (brs, 2H)

Production Example 4: Production of Compound (12)

Under ice cooling, a solution of sodium nitrite (213 mg, 3.10 mmol) in water (7 mL) was slowly added to methyl 2-amino-4-methyl-3,5,6-trifluorobenzoate (678 mg , 3.10mmol) of acetic acid (7mL) and concentrated hydrochloric acid (14mL) mixed solution. The reaction solution was stirred at the same temperature for 50 minutes. Under ice cooling, copper(I) chloride (612 mg, 3.10 mmol) was added to the reaction solution in two portions. After stirring at room temperature for 12 hours, water was added to the reaction liquid, and extraction was performed with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-chloro-4-methyl represented by the following formula [Chem 22] (12) Yl-3,5,6-trifluorobenzoate 505mg:

Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.29 (m, 3H), 3.98 (s, 3H)

Production Example 5: Production of Compound (13)

Under ice cooling, diisobutylaluminum hydride (1.5M toluene solution, 3.5 mL, 5.25 mmol) was dropped to methyl 2-chloro-4-methyl-3,5,6-trifluorobenzoate (502 mg, 2.10 mmol) of a mixed solution of toluene (5 mL) and tetrahydrofuran (5 mL). After stirring for 1 hour under ice cooling, the reaction solution was poured into 1N aqueous hydrochloric acid solution and water, and extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methyl- represented by the following formula [Chem 23](13) 3,5,6-Trifluorobenzyl alcohol 410mg:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.99 (t, 1H), 2.27 (m, 3H), 4.85 (dd, 2H)

Production Example 6: Production of Compound (14)

At room temperature, triethylamine (3.4 mL, 24.53 mmol) and benzylamine (1.73 g, 16.14 mmol) were added dropwise to methyl 4-methoxymethyl-2,3,5,6-tetrafluorobenzene A solution of formate (2.03 g, 8.06 mmol) in toluene (20 mL). After stirring at 100°C for 7 hours, water was added to the reaction liquid, and extraction was performed with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-benzylamino-4 represented by the following formula [Chem 24] (14) -Methoxymethyl-3,5,6-trifluorobenzoate 2.32g:

Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 3.35 (s, 3H), 3.89 (s, 3H), 4.50 (m, 2H), 4.52 (m, 2H), 6.90 (brs, 1H), 7.28 (m, 5H)

Production Example 7: Production of Compound (15)

Add palladium on carbon (230 mg) to methyl 2-benzylamino-4-methoxymethyl-3,5,6-trifluorobenzoate (2.32 g, 6.84 mmol) of acetic acid at room temperature An ethyl acetate (80 mL) solution was used to replace the reaction solution under a hydrogen atmosphere. After stirring at room temperature for 3 hours under a hydrogen atmosphere, the reaction solution was filtered through diatomaceous earth and concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain the following formula [Chem. 25]( 15) Represented methyl 2-amino-4-methoxymethyl-3,5,6-trifluorobenzoate 1.12g: [Chem. 25]

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 3.40 (s, 3H), 3.94 (s, 3H), 4.56 (m, 2H), 5.59 (brs, 2H)

Production Example 8: Production of Compound (16)

Under ice cooling, a solution of sodium nitrite (91 mg, 1.32 mmol) in water (4 mL) was slowly added to methyl 2-amino-4-methoxymethyl-3,5,6-trifluorobenzoic acid A mixed solution of ester (326 mg, 1.31 mmol) in acetic acid (4 mL) and concentrated hydrochloric acid (8 mL). The reaction solution was stirred at the same temperature for 50 minutes. Under ice cooling, copper (I) chloride (259 mg, 2.62 mmol) was added to the reaction solution in two portions. After stirring at room temperature for 5 hours, water was added to the reaction liquid, and extraction was performed with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-chloro-4-methyl represented by the following formula [Chem26](16) Oxymethyl-3,5,6-trifluorobenzoate 135mg:

Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 3.39 (s, 3H), 4.00 (s, 3H), 4.58 (m, 2H)

Production Example 9: Production of Compound (17)

Under ice-cooling, diisobutylaluminum hydride (1.5M toluene solution, 1.0 mL, 1.50 mmol) was dropped to methyl 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzoate (130 mg, 0.48 mmol) of a mixed solution of toluene (3 mL) and tetrahydrofuran (3 mL). After stirring for 1 hour under ice cooling, the reaction solution was poured into 1N aqueous hydrochloric acid solution and water, and extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methoxy represented by the following formula [Chem27](17) Methyl-3,5,6-trifluorobenzyl alcohol 67mg:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.03 (t, 1H), 3.39 (s, 3H), 4.58 (m, 2H), 4.88 (dd, 2H)

Production Example 10: Production of Compound C1 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (54mg, 0.28mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-3, 5,6-trifluorobenzyl alcohol (50mg, 0.26mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (47mg, 0.28 mmol) in chloroform (2 mL). After stirring at room temperature for 24 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-3,5,6 represented by the following formula [Chemical 28](18) -Trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (the present compound C1) 21 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H), 1.26 (s, 3H), 1.46 (d, 1H), 1.69 (s, 3H), 1.70 (s, 3H), 2.08 (t, 1H), 4.87 (d, 1H), 5.28 (m, 2H), 7.07 (m, 1H)

Production Example 11: Production of Compound I1 of the present invention

Pyridine (100mg, 1.20mmol), (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropylmethanyl chloride (76mg, 0.34mmol) And 4-dimethylaminopyridine (3 mg) was added sequentially to a solution (2 mL) of 2-chloro-3,5,6-trifluorobenzyl alcohol (40 mg, 0.20 mmol) in tetrahydrofuran. After stirring at room temperature for 19 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-3,5,6 represented by the following formula [Chem 29](19) -Trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate (Compound I1 of the present invention) 75 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.18 (s, 3H), 1.29 (s, 3H), 1.61 (d, 1H), 2.26 (m, 1H), 5.31 (m, 2H), 5.60 (d, 1H), 7.08 (m, 1H)

Production Example 12: Production of Compound P1 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (53mg, 0.28mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-3, 5,6-trifluorobenzyl alcohol (45mg, 0.23mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (for double bond isomers Ratio: Z/E = about 8/1) (53 mg, 0.34 mmol) in chloroform solution (3 mL). After stirring at room temperature for 20 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-3,5,6 represented by the following formula [Chem 30](20) -Trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (compound P1 of the present invention) (regarding the ratio of double bond isomers: Z/E = about 8/1) 29mg: [Chem 30]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.14 (s, 3H, Z+E body), 1.28 (s, 3H, Z+E body), 1.46 (d, 1H, Z+ E body), 1.70 (dd, 3H, Z+E body), 2.18 (m, 1H, Z+E body), 5.11 (m, 1H, Z+E body), 5.29 (m, 2H, Z+E body) ), 5.60 (m, 1H, Z+E body), 7.08 (m, 1H, Z+E body)

Production Example 13: Production of Compound R1 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (37mg, 0.19mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-3, 5,6-trifluorobenzyl alcohol (31mg, 0.16mmol) and (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethyl A solution of cyclopropanecarboxylic acid (40 mg, 0.19 mmol) in chloroform (2 mL). After stirring at room temperature for 24 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After the organic layer was dried with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-3,5,6 represented by the following formula [Chem 31](21) -Trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate (Compound R1 of the present invention) )33mg: [Chem 31]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.22 (s, 3H), 1.31 (s, 3H), 1.72 (d, 1H), 1.93 (s, 3H), 2.22 (m, 1H), 3.72 (s, 3H), 5.31 (m, 2H), 6.44 (m, 1H), 7.09 (m, 1H)

Production Example 14: Production of Compound T1 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (37mg, 0.19mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-3, 5,6-trifluorobenzyl alcohol (30mg, 0.15mmol) and (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethyl A solution (2 mL) of cyclopropanecarboxylic acid (40 mg, 0.20 mmol) in chloroform. After stirring at room temperature for 24 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-3,5,6 represented by the following formula [Chem 32](22) -Trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate (Compound T1 of the present invention) )47mg: [Chem 32]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.27 (s, 3H), 1.31 (s, 3H), 1.94 (d, 1H), 3.26 (t, 1H), 3.71 (s, 3H), 5.27 (m, 2H), 5.91 (d, 1H), 6.62 (t, 1H), 7.08 (m, 1H)

Production Example 15: Production of Compound W1 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (83mg, 0.43mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-3, A solution of 5,6-trifluorobenzyl alcohol (70 mg, 0.36 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (61 mg, 0.43 mmol) in chloroform (3 mL). After stirring at room temperature for 24 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-3,5,6 represented by the following formula [Chem 33](23) -Trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate (Compound W1 of the present invention) 72 mg:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.17 (s, 7H), 1.25 (s, 6H), 5.24 (m, 2H), 7.08 (m, 1H)

Production Example 16: Production of Compound C2 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (59mg, 0.31mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-4- Methyl-3,5,6-trifluorobenzyl alcohol (50mg, 0.24mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane A chloroform solution (3 mL) of formic acid (52 mg, 0.31 mmol). After stirring at room temperature for 6 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methyl- represented by the following formula [Chem 34](24) 3,5,6-Trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound C2 of the present invention) 53mg :

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H), 1.26 (s, 3H), 1.38 (d, 1H), 1.69 (s, 3H), 1.70 (s, 3H), 2.07 (t, 1H), 2.28 (m, 3H), 4.87 (d, 1H), 5.26 (m, 2H)

Production Example 17: Production of Compound I2 of the present invention

Pyridine (112mg, 1.42mmol), (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropylmethanyl chloride (191mg, 0.36mmol) And 4-dimethylaminopyridine (3 mg) was sequentially added to a solution (2 mL) of 2-chloro-4-methyl-3,5,6-trifluorobenzyl alcohol (50 mg, 0.24 mmol) in tetrahydrofuran. After stirring at room temperature for 7 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methyl- represented by the following formula [Chem 35](25) 3,5,6-Trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate (Compound I2 of the invention) )60mg:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.17 (s, 3H), 1.29 (s, 3H), 1.60 (d, 1H), 2.25 (m, 1H), 2.29 (m, 3H), 5.28 (m, 2H), 5.59 (d, 1H)

Production Example 18: Production of the compound P2 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (49mg, 0.26mmol) and 4-dimethylaminopyridine (2mg) to 2-chloro-4- Methyl-3,5,6-trifluorobenzyl alcohol (41 mg, 0.19 mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (about double bond The ratio of isomers: Z/E = about 8/1) (39 mg, 0.25 mmol) in chloroform solution (3 mL). After stirring at room temperature for 19 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methyl- represented by the following formula [Chem 36](26) 3,5,6-Trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound P2 of the present invention) Structure ratio: Z/E = about 8/1) 24mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.13 (s, 3H, Z+E body), 1.28 (s, 3H, Z+E body), 1.45 (d, 1H, Z+ E body), 1.70 (dd, 3H, Z+E body), 2.17 (m, 1H, Z+E body), 2.28 (m, 3H, Z+E body), 5.11 (m, 1H, Z+E body) ), 5.27 (m, 2H, Z+E body), 5.59 (m, 1H, Z+E body)

Production Example 19: Production of the compound R2 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (41mg, 0.21mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-4- Methyl-3,5,6-trifluorobenzyl alcohol (35mg, 0.17mmol) and (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2, A solution of 3-dimethylcyclopropanecarboxylic acid (46 mg, 0.22 mmol) in chloroform (3 mL). After stirring at room temperature for 21 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methyl- represented by the following formula [Chem 37] (27) 3,5,6-Trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane carboxylate (Compound R2 of the present invention) 58 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.21 (s, 3H), 1.31 (s, 3H), 1.71 (d, 1H), 1.93 (s, 3H), 2.22 (m, 1H), 2.29 (m, 3H), 3.72 (s, 3H), 5.28 (m, 2H), 6.43 (m, 1H)

Production Example 20: Production of Compound T2 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (36mg, 0.19mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-4- Methyl-3,5,6-trifluorobenzyl alcohol (30mg, 0.14mmol) and (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2, A solution (2-mL) of 2-dimethylcyclopropanecarboxylic acid (37 mg, 0.19 mmol) in chloroform. After stirring at room temperature for 14 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methyl- represented by the following formula [Chem 38] (28) 3,5,6-Trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropane carboxylate (Compound T2 of the present invention) 38 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.26 (s, 3H), 1.30 (s, 3H), 1.93 (d, 1H), 2.28 (m, 3H), 3.25 (t, 1H), 3.71 (s, 3H), 5.24 (m, 2H), 5.91 (d, 1H), 6.43 (m, 1H)

Production Example 21: Production of Compound W2 of the invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (41mg, 0.21mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-4- A solution of methyl-3,5,6-trifluorobenzyl alcohol (35 mg, 0.17 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (31 mg, 0.22 mmol) in chloroform (2 mL). After stirring at room temperature for 19 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methyl- represented by the following formula [Chem 39] (29) 3,5,6-Trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate (Compound W2 of the present invention) 49 mg:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.17 (s, 7H), 1.25 (s, 6H), 2.28 (m, 3H), 5.22 (m, 2H)

Production Example 22: Production of Compound C3 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (20mg, 0.10mmol) and 4-dimethylaminopyridine (2mg) to 2-chloro-4- Methoxymethyl-3,5,6-trifluorobenzyl alcohol (16mg, 0.07mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethyl Cyclopropanecarboxylic acid (17 mg, 0.10 mmol) in chloroform (2 mL). After stirring at room temperature for 15 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methoxy represented by the following formula [Chem 40] (30) Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (compound of the present invention) C3) 14mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H), 1.26 (s, 3H), 1.38 (d, 1H), 1.69 (s, 3H), 1.70 (s, 3H), 2.08 (t, 1H), 3.40 (s, 3H), 4.58 (m, 2H), 4.87 (m, 1H), 5.28 (m, 2H)

Production Example 23: Production of Compound I3 of the present invention

Pyridine (130mg, 1.65mmol), (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropylmethanyl chloride (250mg, 0.47mmol) And 4-dimethylaminopyridine (3 mg) was sequentially added to a solution (5 mL) of 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (56 mg, 0.23 mmol) in tetrahydrofuran. After stirring at room temperature for 18 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methoxy represented by the following formula [Chem 41] (31) Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate (this Inventive compound I3) 42 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.18 (s, 3H), 1.29 (s, 3H), 1.60 (d, 1H), 2.26 (m, 1H), 3.40 (s, 3H), 4.58 (m, 2H), 5.30 (m, 2H), 5.59 (d, 1H)

Production Example 24: Production of Compound P3 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (80mg, 0.42mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-4- Methoxymethyl-3,5,6-trifluorobenzyl alcohol (67mg, 0.28mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid ( Regarding the ratio of double bond isomers: Z/E = about 8/1) (64 mg, 0.42 mmol) in chloroform solution (3 mL). After stirring at room temperature for 22 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to silica gel column chromatography to obtain 2-chloro-4-methoxy represented by the following formula [Chem 42] (32) Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (compound P3 of the present invention) (about bis Ratio of bond isomers: Z/E = about 8/1) 25 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.14 (s, 3H, Z+E body), 1.28 (s, 3H, Z+E body), 1.45 (d, 1H, Z+ E body), 1.70 (dd, 3H, Z+E body), 2.18 (m, 1H, Z+E body), 3.40 (s, 3H, Z+E body), 4.58 (m, 2H, Z+E body) ), 5.11 (m, 1H, Z+E body), 5.29 (m, 2H, Z+E body), 5.60 (m, 1H, Z+E body)

Production Example 25: Production of Compound W3 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (60mg, 0.32mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-4- A solution of methoxymethyl-3,5,6-trifluorobenzyl alcohol (50mg, 0.21mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (45mg, 0.32mmol) in chloroform (2mL) ). After stirring at room temperature for 24 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methoxy represented by the following formula [Chem 43] (33) Methyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate (Compound W3 of the invention) 52mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.17 (s, 7H), 1.25 (s, 6H), 3.40 (s, 3H), 4.58 (m, 2H), 5.29 (m, 2H)

Production Example 26: Production of Compound C4 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (67mg, 0.35mmol) and 4-dimethylaminopyridine (4mg) to 2-chloro-4- Ethynyl-3,5,6-trifluorobenzyl alcohol (65mg, 0.29mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane A chloroform solution (3 mL) of formic acid (59 mg, 0.35 mmol). After stirring at room temperature for 17 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was attached to a silica gel column chromatography to obtain 2-chloro-4-ethynyl- represented by the following formula [Chem 44] (34) 3,5,6-Trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound C4 of the present invention) 45mg :

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.13 (s, 3H), 1.27 (s, 3H), 1.38 (d, 1H), 1.69 (s, 3H), 1.70 (s, 3H), 2.07 (t, 1H), 3.66 (s, 1H), 4.87 (d, 1H), 5.28 (m, 2H)

Production Example 27: Production of Compound I4 of the present invention

Pyridine (100mg, 1.27mmol), (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropylmethanyl chloride (191mg, 0.36mmol) And 4-dimethylaminopyridine (3 mg) was sequentially added to a solution (3 mL) of 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl alcohol (40 mg, 0.18 mmol) in tetrahydrofuran. After stirring at room temperature for 19 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was attached to a silica gel column chromatography to obtain 2-chloro-4-ethynyl- represented by the following formula [Chem 45](35) 3,5,6-Trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate (Compound I4 of the present invention) )32mg: [Chem 45]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.18 (s, 3H), 1.30 (s, 3H), 1.61 (d, 1H), 2.26 (m, 1H), 3.67 (s, 1H), 5.29 (m, 2H), 5.60 (d, 1H)

Production Example 28: Production of Compound P4 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (50mg, 0.26mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-4- Ethynyl-3,5,6-trifluorobenzyl alcohol (48mg, 0.22mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (about double bond The ratio of isomers: Z/E = about 8/1) (40 mg, 0.26 mmol) in chloroform solution (3 mL). After stirring at room temperature for 23 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-ethynyl- represented by the following formula [Chem46](36) 3,5,6-Trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound P4 of the present invention) Structure ratio: Z/E = about 8/1) 36 mg: [Chem 46]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H, Z+E body), 1.27 (s, 3H, Z+E body), 1.45 (d, 1H, Z+ E body), 1.79 (dd, 3H, Z+E body), 2.16 (m, 1H, Z+E body), 3.66 (s, 1H, Z+E body), 5.11 (m, 1H, Z+E body) ), 5.26 (m, 2H, Z+E body), 5.58 (m, 1H, Z+E body)

Production Example 29: Production of Compound W4 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (46mg, 0.24mmol) and 4-dimethylaminopyridine (3mg) to 2-chloro-4- A solution of ethynyl-3,5,6-trifluorobenzyl alcohol (45 mg, 0.20 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (34 mg, 0.24 mmol) in chloroform (3 mL). After stirring at room temperature for 25 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-ethynyl- represented by the following formula [Chem 47] (37) 3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate (Compound W4 of the present invention) 28 mg: [Chem. 47]

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.18 (s, 7H), 1.26 (s, 6H), 3.66 (s, 1H), 5.23 (m, 2H)

Production Example 30: Production of Compound M2 of the present invention

。 Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (55mg, 0.286mmol) and 4-dimethylaminopyridine (5mg) to 2-chloro-4- Methyl-3,5,6-trifluorobenzyl alcohol (40mg, 0.190mmol) and (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propene Base]-2,2-dimethylcyclopropanecarboxylic acid (46 mg, 0.190 mmol) in chloroform (2 mL). After stirring at room temperature for 17 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-chloro-4-methyl- represented by the following formula [Chem48](38) 3,5,6-Trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethyl Cyclopropane carboxylate (Compound M2 of the present invention) 63mg:

.

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.29 (s, 3H), 1.30 (s, 3H), 1.97 (d, 1H), 2.17 (m, 1H), 2.29 (m, 3H), 5.27 (m, 2H), 6.89 (d, 1H)

Next, the preparation examples are shown. In addition, part means mass part.

Preparation Example 1

Dissolve 0.1 parts of each compound of the invention C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4 and W4 10 parts of xylene was mixed with 89.9 parts of deodorized kerosene to obtain an oil agent.

Preparation Example 2

Mix and dissolve each of the compounds C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4 and W4 of the present invention 0.1 parts and 39.9 parts of deodorized kerosene are filled in an aerosol container. After the valve part is installed, 60 parts of the propellant (liquefied petroleum gas) are pressurized and filled through the valve part to obtain an oily spray can.

Preparation Example 3

Mix and dissolve each of the compounds C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4 and W4 of the present invention 0.6 parts, 5 parts of xylene, 3.4 parts of deodorized kerosene, and 1 part of RHEODOL MO-60 (emulsifier, registered trademark of Kao Co., Ltd.), filled with 50 parts of water in a spray can container, and filled under pressure through a valve 40 parts of propellant (liquefied petroleum gas) were used to obtain an aqueous spray can.

Preparation Example 4

0.3g each of the compounds C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4 and W4 of the present invention and 0.5g of BHT was evenly mixed and mixed with 99.2g of the base material for mosquito coils (the mixture of pyrethrum extract grains, wood powder, red ash powder and starch), and the mixture containing malachite green as a coloring agent was added 100mL of water, after fully kneaded, the product was shaped and dried to obtain a mosquito coil.

Preparation Example 5

Add deodorized kerosene to the compounds C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4 and W4 Each 0.8g, piperonyl butoxide 0.4g and the dye were dissolved and dissolved in 10mL. 0.5 mL of this solution was uniformly impregnated with a base material for mosquito coils of 22 mm×35 mm and a thickness of 2.8 mm (those in which fibrils of a mixture of cotton seed wool and pulp were coagulated into a plate shape) to obtain mosquito coil tablets.

Preparation Example 6

The compounds of the invention C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4 and W4 each 0.7 parts and 0.3 parts of BHT dissolved in 50 parts of surfactant (diethylene glycol monobutyl ether) and 49 parts of purified water were placed in a polyester container, and a heater (heater) ) The liquid-absorbent wick heated by the upper part (who burned the inorganic powder) to obtain an aqueous mosquito repellent used in the heating evapotranspiration device.

Preparation Example 7

The compounds of the invention C1, I1, P1, R1, T1, W1, C2, I2, After 3.0 parts each of M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4, and W4, 3.0 parts of oxadiazon, and 94.0 parts of azodimethanamide, mix them 20g is filled into a plastic film bag, stored in a heat-resistant container and filled with an igniter to obtain a smoker.

Preparation Example 8

10 mg each of the compounds C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4 and W4 of the present invention were dissolved in Appropriate amount of acetone is evenly coated on a non-woven fabric of 5 cm×5 cm and a thickness of 0.3 mm, and then the acetone is air-dried to obtain a room temperature dispersant.

Preparation Example 9

The compound of the present invention C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, P4 and W4 each 10 parts, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt and 55 parts of water are mixed and finely pulverized by a wet pulverization method to obtain a 10% flow Agent.

Next, it was shown that the compound of the present invention was effectively used as an active ingredient of a pest control agent as a test example.

Effect test example 1 (contact test using Culex pipiens pallens)

0.05 mL of 0.2% acetone solution containing 0.1 mg of the compounds of the present invention C1, I1, P1, R1, T1, W1, C4, I4, P4 and W4 was dropped to a culture of 28 mm in diameter, 13 mm internal height and 6.15 cm ² bottom area After the petri dish spreads evenly on the bottom surface, the acetone is removed with a double ball. Six females of Culex pipiens pallens were placed in petri dishes where each sample was held on the bottom surface, and the upper side was covered with a perforated film. The number of knock-downs was recorded every 1 minute, and the KT _{50 was} measured and recorded ( 50% knockdown time) and lethality after 24 hours. For the sample system showing the above-mentioned value for the knockdown rate, acetone was added to the aforementioned 0.2% acetone solution to dilute it 10 times as a 0.02% acetone solution, and the aforementioned various instruments (petri dishes) and test methods were repeated in sequence. .

Furthermore, as a comparative control, pyrethrin was used: 1,3,4,5,6,7-hexahydro-1,3-dioxo-2H-isoindol-2-yl(1R)-trans, cis The formula-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (hereinafter referred to as Comparative Compound A) was tested in the same manner.

Show the results in Table 1

【Table 1】

As a result of the test, it was found that the compounds C1, I1, P1, R1, T1, W1, C4, I4, P4 and W4 of the present invention all showed a higher knock-down activity than that of the comparative compound A (Pyrethrin) .

Effect test example 2 (contact test using Culex pipiens pallens)

0.05 mL of 0.2% acetone solution containing 0.1 mg of the compounds of the present invention C2, I2, P2, R2, T2, W2, C3, I3, P3 and W3 was dropped to a culture of 28 mm diameter, 13 mm internal height and 6.15 cm ² bottom area After the dish spreads evenly on the bottom surface, the acetone is removed with a double ball. Six females of Culex pipiens pallens were placed in petri dishes where each sample was held on the bottom surface, and the upper side was covered with a perforated membrane. The number of knockdowns was recorded every 1 minute, and KT ₅₀ (50% knocked down) was measured and recorded. Time) and lethality after 24 hours. For the sample system showing the above-mentioned value for the knockdown rate, acetone was added to the aforementioned 0.2% acetone solution to dilute it 10 times as a 0.02% acetone solution, and the aforementioned various instruments (petri dishes) and test methods were repeated in sequence. .

Furthermore, as a comparative control, pyrethrin was used: 1,3,4,5,6,7-hexahydro-1,3-dioxo-2H-isoindol-2-yl(1R)-trans, cis The formula-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (hereinafter referred to as Comparative Compound A) was tested in the same manner.

Display the results in Table 2

【Table 2】

As a result of the test, it was found that the compounds C2, I2, P2, R2, T2, W2, C3, I3, P3, and W3 of the present invention all exhibited a higher knockdown rate than that of Comparative Compound A (Pyrethrin).

Effect test example 3 (normal temperature swellability test using Culex pipiens pallens)

Ten female Culex pipiens pallens were placed in a petri dish with a diameter of 9 cm, an internal height of 1.9 cm, and a bottom area of 63.6 cm ² , and were covered with a 16-mesh wire mesh. 0.5 mL of a 2% acetone solution of the compound I1, P1, W1, I2, P2, W2, I3, P3, W3, P4 and W4 containing 0.09 mg of the prepared agent was dropped into a Petri dish of the same size (diameter 9cm, inner height 1.9cm, bottom area 63.6cm ² ), air-dried acetone. Next, the petri dish coated with the medicine was placed upside down on the wire mesh. Then, every 1 minute, the number of female adults of Culex pipiens pallens knocked down was investigated to find the knockdown rate.

Furthermore, as a comparative control, 2-chloro-6-fluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate represented by the following formula [Chem 49] (39) (Japanese Patent Publication 57-165343. The compound described in Gazette No. 57-165343. The following is referred to as Comparative Compound B) and Yiyining: (RS)-(EZ)-1-ethynyl-2-methyl-2-pentenyl (1R)-trans The formula, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (hereinafter referred to as comparative compound C), was similarly tested.

The results are shown in Table 3

【table 3】

As a result of the test, it is known that the compounds of the present invention I1, P1, W1, I2, P2, W2, I3, P3, W3, P4 and W4 all show more than the comparative compounds High knockdown rate of Compound B and Comparative Compound C (Yininging).

Effect test example 4 (insecticide test using mosquito coils)

Approximately 50 adults of Culex pipiens pallens were released into a 70 cm cubic glass chamber, and a small battery-type fan (with a blade diameter of 13 cm) was installed in the chamber and rotated. First, after igniting both ends of 0.1g of the mosquito coils of the compounds C1, I1, P1, R1, T1, C2, I2, M2, P2, R2, C3, I3, P3, C4 and I4 obtained in Preparation Example 4 Putting it in a glass box can knock down more than 80% of Culex pipiens pallens within 15 minutes and kill more than 80% on the next day.

Effect test example 5 (insecticide test using smoke agent)

In a 6-tatami room, the compound C1, I1, P1, R1, T1, C2, I2, M2, P2, R2, T2, C3, I3, P3, C4, I4 and the compound of the present invention prepared according to Preparation Example 7 were prepared using a heater As a result of heating a bag of P4 smoker to about 250°C, the components spread from the smoke hole formed by a plastic film to the entire room. For household dusts such as cockroaches, fleas, and bed bugs, and house dust mites or carrion mites, etc. The control of mites (house-dust mites) is also effective.

Effect test example 6 (insecticide test using spray can)

Approximately 30 female adults of housefly were released into a 60 cm cubic glass box, and the compound C1, I1, P1, R1, T1, W1 of the present invention obtained by Formulation Example 2 every second from the hole in the side wall of the box C2, I2, M2, P2, R2, T2, W2, I3, P3, I4 and P4 spray can spray. As a result, it was possible to knock down 100% of house flies within 2 minutes, and it was confirmed that the compound of the present invention had a high knockdown effect.

<Example of Br-containing ester compound>

A production example of the compound of the present invention (Br-containing ester compound) is shown.

Production Example 1: Production of Compound (X)

At room temperature, tetrabutylammonium bromide (1440mg, 4.47mmol), camphorsulfonic acid (624mg, 2.69mmol), sodium nitrite (186mg, 2.69mmol), divalent copper bromide (5mg, 0.02mmol) were added in sequence A solution of methyl 2-amino-3,5,6-trifluorobenzoate (558 mg, 2.72 mmol) in acetonitrile (25 mL). After stirring at 60°C for 24 hours, water was added to the reaction liquid at room temperature, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-bromo-3,5 represented by the following formula [Chem 50](X) ,6-Trifluorobenzoate 340mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 4.00 (s, 3H), 7.16 (m, 1H)

Production Example 2: Production of Compound (XI)

Diisobutylaluminum hydride (1.5M toluene solution, 2.8mL, 4.19mmol) was dropped into toluene of methyl 2-bromo-3,5,6-trifluorobenzoate (340mg, 1.27mmol) under ice cooling. (4mL) and a mixture of tetrahydrofuran (4mL). After stirring under ice cooling for 2 hours, the reaction solution was poured into 1N hydrochloric acid aqueous solution and water, and extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-3,5,6 represented by the following formula [Chem 51](XI) -262mg of trifluorobenzyl alcohol:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.04 (t, 1H), 4.85 (dd, 2H), 7.04 (m, 1H)

Production Example 3: Production of Compound (XII)

Triethylamine (1.9mL, 13.65mmol) and benzylamine (1.00g, 9.33mmol) were added dropwise to methyl 4-methyl-2,3,5,6-tetrafluorobenzoate at room temperature (1.01 g, 4.55 mmol) in toluene (15 mL). After stirring at 100°C for 10 hours, water was added to the reaction liquid, and extraction was performed with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-benzylamino-4 represented by the following formula [Chem 52] (XII) -Methyl-3,5,6-trifluorobenzoate 1.18g: [Chemical 52]

Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.21 (m, 3H), 3.88 (s, 3H), 4.50 (m, 2H), 6.96 (brs, 1H), 7.29 (m, 5H)

Production Example 4: Production of Compound (XIII)

。 Palladium-carbon (117 mg) was added to methyl 2-benzylamino-4-methyl-3,5,6-trifluorobenzoate (1.15 g, 3.72 mmol) of ethyl acetate at room temperature ( 50mL) solution, replacing the reaction solution in a hydrogen environment. After stirring at room temperature for 3 hours under a hydrogen atmosphere, the reaction solution was filtered through diatomaceous earth, concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain the following formula [Chem 53] ( XIII) methyl 2-amino-4-methyl-3,5,6-trifluorobenzoate 690mg:

.

Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.24 (m, 3H), 3.92 (s, 3H), 5.55 (brs, 2H)

Production Example 5: Production of Compound (XIV)

At room temperature, tetrabutylammonium bromide (1867mg, 5.80mmol), camphorsulfonic acid (809mg, 3.49mmol), sodium nitrite (290mg, 4.20mmol), divalent copper bromide (18mg, 0.08mmol) were added in sequence A solution of methyl 2-amino-4-methyl-3,5,6-trifluorobenzoate (637 mg, 2.91 mmol) in acetonitrile (30 mL). After stirring at 60°C for 24 hours, water was added to the reaction liquid at room temperature, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-bromo-4-methyl represented by the following formula [Chem 54] (XIV) Benzyl-3,5,6-trifluorobenzoate 354mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.30 (m, 3H), 3.98 (s, 3H)

Production Example 6: Production of Compound (XV)

Under ice-cooling, diisobutylaluminum hydride (1.5M toluene solution, 2.5 mL, 3.75 mmol) was dropped to methyl 2-bromo-4-methyl-3,5,6-trifluorobenzoate (354 mg, 1.25 mmol) of a mixed solution of toluene (3 mL) and tetrahydrofuran (3 mL). After stirring under ice cooling for 2 hours, the reaction solution was poured into 1N hydrochloric acid aqueous solution and water, and extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methyl- represented by the following formula [Chem 55] (XV) 3,5,6-Trifluorobenzyl alcohol 278mg:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.05 (t, 1H), 2.28 (m, 3H), 4.86 (dd, 2H)

Production Example 7: Production of Compound (XVI)

At room temperature, triethylamine (3.4 mL, 24.53 mmol) and benzylamine (1.73 g, 16.14 mmol) were added dropwise to methyl 4-methoxymethyl-2,3,5,6-tetrafluorobenzene A solution of formate (2.03 g, 8.06 mmol) in toluene (20 mL). After stirring at 100°C for 7 hours, water was added to the reaction liquid, and extraction was performed with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-benzylamino-4 represented by the following formula [Chem 56] (XVI) -Methoxymethyl-3,5,6-trifluorobenzoate 2.32g:

Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 3.35 (s, 3H), 3.89 (s, 3H), 4.50 (m, 2H), 4.52 (m, 2H), 6.90 (brs, 1H), 7.28 (m, 5H)

Production Example 8: Production of Compound (XVII)

Add palladium on carbon (230 mg) to methyl 2-benzylamino-4-methoxymethyl-3,5,6-trifluorobenzoate (2.32 g, 6.84 mmol) of acetic acid at room temperature An ethyl acetate (80 mL) solution was used to replace the reaction solution under a hydrogen atmosphere. After stirring at room temperature for 3 hours under a hydrogen atmosphere, the reaction solution was filtered through diatomaceous earth and concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain the following formula [Chem 57] ( XVII) represented by methyl 2-amino-4-methoxymethyl-3,5,6-trifluorobenzoate 1.12g: [Chem 57]

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 3.40 (s, 3H), 3.94 (s, 3H), 4.56 (m, 2H), 5.59 (brs, 2H)

Production Example 9: Production of Compound (XVIII)

At room temperature, tetrabutylammonium bromide (811mg, 2.52mmol), camphorsulfonic acid (351mg, 1.51mmol), sodium nitrite (104mg, 1.51mmol), divalent copper bromide (5mg, 0.02mmol) were added in sequence A solution of methyl 2-amino-4-methoxymethyl-3,5,6-trifluorobenzoate (314 mg, 1.26 mmol) in acetonitrile (15 mL). After stirring at 60°C for 24 hours, water was added to the reaction liquid at room temperature, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain methyl 2-bromo-4-methyl represented by the following formula [Chem 58] (XVIII) Oxymethyl-3,5,6-trifluorobenzoate 121mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 3.39 (s, 3H), 4.00 (s, 3H), 4.59 (m, 2H)

Production Example 10: Production of Compound (XIX)

Diisobutylaluminum hydride (1.5M toluene solution, 0.8mL, 1.20mmol) was added dropwise to methyl 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzoate under ice cooling (121 mg, 0.39 mmol) of a mixed solution of toluene (2 mL) and tetrahydrofuran (2 mL). After stirring under ice cooling for 2 hours, the reaction solution was poured into 1N hydrochloric acid aqueous solution and water, and extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methoxy represented by the following formula [Chem 59] (XIX) Methyl-3,5,6-trifluorobenzyl alcohol 69mg:

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.08 (t, 1H), 3.39 (s, 3H), 4.58 (m, 2H), 4.89 (dd, 2H)

Production Example 11: Production of Compound 3 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (59mg, 0.31mmol) and 4-dimethylaminopyridine (2mg) to 2-bromo-3, 5,6-trifluorobenzyl alcohol (49mg, 0.20mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (51mg, 0.30 mmol) in chloroform (3 mL). After stirring at room temperature for 19 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-3,5,6 represented by the following formula [Chem 60](XX) -Trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound 3 of the present invention) 17 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H), 1.27 (s, 3H), 1.39 (d, 1H), 1.68 (s, 3H), 1.71 (s, 3H), 2.08 (t, 1H), 4.88 (m, 1H), 5.29 (m, 2H), 7.06 (m, 1H)

Production Example 12: Production of Compound 9 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (91mg, 0.47mmol) and 4-dimethylaminopyridine (3mg) to 2-bromo-3, 5,6-trifluorobenzyl alcohol (88mg, 0.37mmol) and (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylic acid (99mg , 0.48mmol) in chloroform (3mL). After stirring at room temperature for 18 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-3,5,6 represented by the following formula [Chem61](XXI) -Trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate (Compound 9 of the present invention) 118 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.18 (s, 3H), 1.29 (s, 3H), 1.61 (d, 1H), 2.27 (m, 1H), 5.31 (m, 2H), 5.60 (d, 1H), 7.09 (m, 1H)

Production Example 13: Production of Compound 16 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (50mg, 0.26mmol) and 4-dimethylaminopyridine (3mg) to 2-bromo-3, 5,6-trifluorobenzyl alcohol (41 mg, 0.17 mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (for double bond isomers) Ratio: Z/E = about 8/1) (40 mg, 0.26 mmol) in chloroform solution (3 mL). After stirring at room temperature for 24 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-3,5,6 represented by the following formula [Chem62](XXII) -Trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound 16 of the present invention) (regarding the ratio of isomers of double bonds: Z/E=about 8/1) 32mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H, Z+E body), 1.27 (s, 3H, Z+E body), 1.46 (d, 1H, Z+ E body), 1.71 (dd, 3H, Z+E body), 2.18 (m, 1H, Z+E body), 5.12 (m, 1H, Z+E body), 5.30 (m, 2H, Z+E body) ), 5.62 (m, 1H, Z+E body), 7.07 (m, 1H)

Production Example 14: Production of Compound 23 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (44mg, 0.23mmol) and 4-dimethylaminopyridine (3mg) to 2-bromo-3, A solution of 5,6-trifluorobenzyl alcohol (35 mg, 0.15 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (33 mg, 0.23 mmol) in chloroform (2 mL). After stirring at room temperature for 20 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-3,5,6 represented by the following formula [Chem63](XXIII) -Trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate (Compound 23 of the present invention) 28 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.17 (s, 7H), 1.25 (s, 6H), 5.32 (m, 2H), 7.06 (m, 1H)

Production Example 15: Production of Compound 26 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (34mg, 0.18mmol) and 4-dimethylaminopyridine (2mg) to 2-bromo-4- Methyl-3,5,6-trifluorobenzyl alcohol (30mg, 0.12mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane Formic acid (30 mg, 0.18 mmol) in chloroform (2 mL). After stirring at room temperature for 20 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methyl- represented by the following formula [Chem64](XXIV) 3,5,6-Trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound 26 of the present invention) 22 mg : [Chem64]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H), 1.27 (s, 3H), 1.38 (d, 1H), 1.69 (s, 3H), 1.70 (s, 3H), 2.08 (t, 1H), 2.29 (m, 3H), 4.88 (m, 1H), 5.26 (m, 2H)

Production Example 16: Production of Compound 32 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (35mg, 0.18mmol) and 4-dimethylaminopyridine (3mg) to 2-bromo-4- Methyl-3,5,6-trifluorobenzyl alcohol (30mg, 0.12mmol) and (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethyl A solution (2 mL) of cyclopropanecarboxylic acid (37 mg, 0.18 mmol) in chloroform. After stirring at room temperature for 16 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methyl- represented by the following formula [Chem 65] (XXV) 3,5,6-Trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate (Compound 32 of the present invention) )35mg: [Chem 65]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.17 (s, 3H), 1.29 (s, 3H), 1.60 (d, 1H), 2.27 (m, 1H), 2.29 (m, 3H), 5.28 (m, 2H), 5.59 (d, 1H)

Production Example 17: Production of Compound 39 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (82mg, 0.43mmol) and 4-dimethylaminopyridine (5mg) to 2-bromo-4- Methyl-3,5,6-trifluorobenzyl alcohol (84mg, 0.33mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (about double bond The ratio of isomers: Z/E = about 8/1) (66 mg, 0.43 mmol) in chloroform solution (3 mL). After stirring at room temperature for 18 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methyl- represented by the following formula [Chem 66] (XXVI) 3,5,6-Trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound 39 of the present invention) Structure ratio: Z/E = about 8/1) 42mg: [Chem 66]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.13 (s, 3H, Z+E body), 1.28 (s, 3H, Z+E body), 1.45 (d, 1H, Z+ E body), 1.70 (dd, 3H, Z+E body), 2.18 (m, 1H, Z+E body), 2.29 (m, 3H, Z+E body), 5.12 (m, 1H, Z+E body) ), 5.28 (m, 2H, Z+E body), 5.59 (m, 1H, Z+E body)

Production Example 18: Production of Compound 46 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (29mg, 0.15mmol) and 4-dimethylaminopyridine (3mg) to 2-bromo-4- A solution of methyl-3,5,6-trifluorobenzyl alcohol (25 mg, 0.10 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (21 mg, 0.15 mmol) in chloroform (2 mL). After stirring at room temperature for 22 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methyl- represented by the following formula [Chem67](XXVII) 3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate (Compound 46 of the present invention) 18 mg: [Chem 67]

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.16 (s, 7H), 1.24 (s, 6H), 2.28 (m, 3H), 5.32 (m, 2H)

Production Example 19: Production of Compound 49 of the present invention

。 Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (70mg, 0.36mmol) and 4-dimethylaminopyridine (2mg) to 2-bromo-4- Methoxymethyl-3,5,6-trifluorobenzyl alcohol (69mg, 0.24mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethyl Cyclopropanecarboxylic acid (80 mg, 0.48 mmol) in chloroform (2 mL). After stirring at room temperature for 23 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methoxy represented by the following formula [Chem 68](XXVIII) Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (compound of the present invention) 49) 17mg:

.

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H), 1.27 (s, 3H), 1.38 (d, 1H), 1.69 (s, 3H), 1.71 (s, 3H), 2.08 (t, 1H), 3.40 (s, 3H), 4.59 (m, 2H), 4.88 (m, 1H), 5.29 (m, 2H)

Production Example 20: Production of Compound 55 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (49mg, 0.26mmol) and 4-dimethylaminopyridine (3mg) to 2-bromo-4- Methoxymethyl-3,5,6-trifluorobenzyl alcohol (48mg, 0.17mmol) and (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2- A solution (2 mL) of dimethylcyclopropanecarboxylic acid (53 mg, 0.25 mmol) in chloroform. After stirring at room temperature for 20 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to silica gel column chromatography to obtain 2-bromo-4-methoxy represented by the following formula [Chem 69] (XXIX) Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane carboxylate (this Inventive compound 55) 66mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.18 (s, 3H), 1.29 (s, 3H), 1.60 (d, 1H), 2.26 (m, 1H), 3.40 (s, 3H), 4.59 (m, 2H), 5.31 (m, 2H), 5.60 (d, 1H)

Production Example 21: Production of Compound 62 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (38mg, 0.20mmol) and 4-dimethylaminopyridine (3mg) to 2-bromo-4- Methoxymethyl-3,5,6-trifluorobenzyl alcohol (36mg, 0.13mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid ( Regarding the ratio of isomers of double bonds: Z/E = about 8/1) (30 mg, 0.20 mmol) in chloroform solution (3 mL). After stirring at room temperature for 18 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methoxy represented by the following formula [Chem 70](XXX) Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane carboxylate (Compound 62 of the present invention) (about bis Ratio of bond isomers: Z/E = about 8/1) 22 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.12 (s, 3H, Z+E body), 1.26 (s, 3H, Z+E body), 1.46 (d, 1H, Z+ E body), 1.71 (dd, 3H, Z+E body), 2.18 (m, 1H, Z+E body), 3.40 (s, 3H, Z+E body), 4.58 (m, 2H, Z+E body) ), 5.11 (m, 1H, Z+E body), 5.30 (m, 2H, Z+E body), 5.61 (m, 1H, Z+E body)

Production Example 22: Production of Compound 69 of the present invention

Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (30mg, 0.16mmol) and 4-dimethylaminopyridine (3mg) to 2-bromo-4- A solution of methoxymethyl-3,5,6-trifluorobenzyl alcohol (30mg, 0.11mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (23mg, 0.16mmol) in chloroform (2mL) ). After stirring at room temperature for 24 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure, and the residue was added to a silica gel column chromatography to obtain 2-bromo-4-methoxy represented by the following formula [Chem71] (XXXI) Methyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropane carboxylate (Compound 69 of the present invention) 18 mg:

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.17 (s, 7H), 1.25 (s, 6H), 3.40 (s, 3H), 4.59 (m, 2H), 5.30 (m, 2H)

Next, the preparation examples are shown. In addition, part means mass part.

Preparation Example 1

0.1 parts of each of the compounds 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 of the present invention were dissolved in 10 parts of xylene and mixed with 89.9 parts of deodorized kerosene to obtain oil Agent.

Preparation Example 2

The spray can container was filled with 0.1 parts of each of the compounds of the present invention mixed with 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 and 39.9 parts of deodorized kerosene. After the valve portion, 60 parts of a propellant (liquefied petroleum gas) was pressurized and filled through the valve portion to obtain an oily spray can.

Preparation Example 3

0.6 parts of each of the compounds 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 of the present invention were mixed and dissolved, 5 parts of xylene, 3.4 parts of deodorized kerosene and RHEODOL MO-60 (Emulsifier, registered trademark of Kao Co., Ltd.) 1 part is filled with 50 parts of water in a spray can container, and 40 parts of a propellant (liquefied petroleum gas) is pressurized and filled through a valve part to obtain an aqueous spray can.

Preparation Example 4

0.3 g of each of the compounds 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 and 0.5 g of BHT were evenly mixed and mixed on the base material for mosquito coils (with pyrethrum extract mixed) After 99.2g of gluten powder, wood powder, red powder and starch), 100mL of water containing malachite green as a coloring agent was added, and the material after thorough kneading was molded and dried to obtain a mosquito coil.

Preparation Example 5

Add deodorized kerosene to each of the compounds of the present invention 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 0.8g, piperonyl butoxide 0.4g and Dye and dissolve, all in 10mL. 0.5 mL of this solution was uniformly impregnated with a base material for mosquito coils of 22 mm×35 mm and a thickness of 2.8 mm (those in which fibrils of a mixture of cotton seed wool and pulp were coagulated into a plate shape) to obtain mosquito coil tablets.

Preparation Example 6

0.7 parts of each of the compounds of the present invention 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 and 0.3 part of BHT were dissolved in a surfactant (diethylene glycol monobutyl ether) 50 parts of the liquid agent obtained from 49 parts of purified water is put into a polyester container, and by inserting a liquid-absorbing core that can heat the upper part with a heater (the inorganic powder is sintered), the liquid used in the heating evapotranspiration device is obtained. Water-based mosquito repellent.

Preparation Example 7

After fully mixing 3.0 parts of each of the compounds of the present invention 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69, 3.0 parts of oxadiazon and 94.0 parts of azodimethanamide, Fill 20g of it into a plastic film bag, store it in a heat-resistant container and fill it with an igniter to obtain a smoker.

Preparation Example 8

Dissolve 10 mg of each of the compounds of the present invention 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 in an appropriate amount of acetone, and uniformly apply to a non-woven fabric of 5 cm x 5 cm and a thickness of 0.3 mm , Air-dried acetone to get room temperature dispersant.

Preparation Example 9

10 parts of each of the compounds 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether ammonium sulfate, and 55 parts of water was mixed and finely pulverized by a wet pulverization method to obtain a 10% flowable agent.

Next, it was shown that the compound of the present invention was effectively used as an active ingredient of a pest control agent as a test example.

Effect test example 1 (contact test using Culex pipiens pallens)

0.05 mL of 0.2% acetone solution containing 0.1 mg of compounds of the present invention 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 was dropped to a diameter of 28 mm, an internal height of 13 mm, and a bottom area of 6.15 After the cm ² petri dish spreads evenly on the bottom surface, the acetone is removed with a double ball. Six females of Culex pipiens pallens were placed in petri dishes where each sample was held on the bottom surface, and the upper side was covered with a perforated membrane. The number of knockdowns was recorded every 1 minute, and KT ₅₀ (50% knocked down) was measured and recorded. Time) and lethality after 24 hours. For the sample system showing the above-mentioned value for the knockdown rate, acetone was added to the aforementioned 0.2% acetone solution to dilute it 10 times as a 0.02% acetone solution, and the aforementioned various instruments (petri dishes) and test methods were repeated in sequence. .

Furthermore, as a comparative control, pyrethrin was used: 1,3,4,5,6,7-hexahydro-1,3-dioxo-2H-isoindol-2-yl(1R)-trans, cis The formula-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate (hereinafter referred to as Comparative Compound A) was tested in the same manner.

Show the results in Table 4

【Table 4】

As a result of the test, it was found that the compounds 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62, and 69 of the present invention all exhibited a higher knockdown rate than that of Comparative Compound A (Pyrethrin).

Effect Test Example 2 (Normal volatility test using Culex pipiens pallens)

Ten females of Culex pipiens pallens were placed in culture blood with a diameter of 9 cm, an internal height of 1.9 cm, and a bottom area of 63.6 cm ² , which was covered with a 16-mesh wire mesh. 0.5 mL of 2% acetone solutions of the compounds 23, 46 and 69 of the present invention containing 0.09 mg of the prepared agent was dropped into a petri dish of the same size (diameter 9 cm, internal height 1.9 cm, bottom area 63.6 cm ² ) Air dry. Next, the petri dish coated with the medicine was placed upside down on the wire mesh. Then, every 1 minute, the number of female adults of Culex pipiens pallens knocked down was investigated to find the knockdown rate.

Also, as a comparative control, Essolin: (RS)-(EZ)-1-ethynyl-2-methyl-2-pentenyl (1R)-trans, cis-3-(2-methyl (-1-propenyl)-2,2-dimethylcyclopropane carboxylate (hereinafter referred to as Comparative Compound B), and the same test was conducted.

Show the results in Table 5

As a result of the test, it was found that the compounds 23, 46 and 69 of the present invention all showed a higher knockdown rate than that of the comparative compound B (Yininging).

Effect test example 3 (insecticide test using mosquito coils)

Approximately 50 adults of Culex pipiens pallens were released into a 70 cm cubic glass box, and a small battery-type fan (with a blade diameter of 13 cm) was installed in the box to rotate it. First, 0.1g of the mosquito coils of the compounds 3, 9, 16, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 of the present invention obtained in Preparation Example 4 were ignited at both ends and placed in a glass box. Within 15 minutes can make more than 80% of the light color Culex mosquitoes are knocked down and can kill more than 80% the next day.

Example 4 of effect test (insecticide test using smoke agent)

In a 6-tatami room, use a heater to heat 1 bag of the fumigant of Compounds 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 prepared according to Preparation Example 7 to about As a result of the temperature of 250°C, the components spread from the smoke holes formed by the plastic film to the entire room, and it is also effective for the prevention of house dust mites such as cockroaches, fleas, bed bugs, and house dust mites or carrion mites.

Example 5 of effect test (insecticide test using spray can)

Approximately 30 female housefly adults were released into a 60 cm cubic glass box, and the compound 3, 9, 16, 16, 23, 26, 32 of the present invention obtained by Formulation Example 2 was taken from the hole in the side wall of the box every second. Spray in spray cans of 39, 46, 49, 55, 62 and 69. As a result, it was possible to knock down 100% of house flies within 2 minutes, and it was confirmed that the compound of the present invention had a high knockdown effect.

Because the compound of the present invention has an excellent pest control effect, it can be used as an effective component of a pest control agent. In addition, the compound of the present invention has the possibility of being used as an active ingredient of a control agent against a pest that has acquired resistance, and is extremely effective.

Claims (6)

An ester compound, represented by the following general formula [Chem 1] (1):

[In the formula, R ¹ represents a hydrogen atom, and R ² is represented by the following general formula [Chem 2] (2)

(Here X and Y are the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or a C 1-4 alkyl group, X represents a hydrogen atom, Y represents a C 1-4 alkyl group, X represents a halogen When an atom, a cyano group, or an alkyl group having 1 to 4 carbon atoms, Y represents a halogen atom or an alkyl group having 1 to 4 carbon atoms), and R ³ represents a hydrogen atom, a trifluoromethyl group, a methyl group, Methoxy, methoxymethyl, allyl, ethynyl or propynyl]. An ester compound represented by the following general formula [Chem 3] (I): [Chem 3]

[Where R ¹ represents a hydrogen atom, and R ² is represented by the following general formula [Chem 4] (II)

(Here X and Y are the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or a C 1-4 alkyl group, X represents a hydrogen atom, Y represents a C 1-4 alkyl group, X represents a halogen When an atom, a cyano group, or an alkyl group having 1 to 4 carbon atoms, Y represents a halogen atom or an alkyl group having 1 to 4 carbon atoms), and R ³ represents a hydrogen atom, trifluoromethyl, methyl, Methoxy, methoxymethyl, allyl, ethynyl or propynyl]. For example, the ester compound of the first or second patent application, wherein R ³ is represented by a hydrogen atom, a methyl group, or a methoxymethyl group. An ester compound, represented by the following chemical formula [Chem 48] (38):

. A pest control agent containing an ester compound taking any one of the first, second, or fourth patent application scope as an active ingredient. A pest control method, applying the ester compound of any one of the first, second, or fourth items of the patent application to a pest or a pest habitat, the pest control method is excluded from use in humans Or animals.