TW201739353A - Ester compounds and use thereof - Google Patents

Ester compounds and use thereof Download PDF

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TW201739353A
TW201739353A TW106111751A TW106111751A TW201739353A TW 201739353 A TW201739353 A TW 201739353A TW 106111751 A TW106111751 A TW 106111751A TW 106111751 A TW106111751 A TW 106111751A TW 201739353 A TW201739353 A TW 201739353A
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compound
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methyl
trifluorobenzyl
trans
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TW106111751A
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TWI687161B (en
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Noritada Matsuo
Yasuyuki Koutani
Koji Nakayama
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Dainihon Jochugiku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
    • C07C69/747—Chrysanthemumic acid esters

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The purpose of the present invention is to provide a compound having excellent pest controlling efficacy. An ester compound represented by general formula (1) [wherein R1 represents a hydrogen atom or a methyl group, R2 represents a methyl group when R1 represents a methyl group and R2 represents a group represented by general formula (2) (wherein X and Y may be the same as or different from each other, and independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms) when R1 represents a hydrogen atom, and R3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group]; a pest controlling agent which is prepared using the ester compound; and a method for controlling a pest using the ester compound.

Description

酯化合物及其用途Ester compound and its use

本發明是關於酯化合物以及使用該酯化合物的害蟲防除劑及害蟲防除方法。The present invention relates to an ester compound and a pest controlling agent and a pest controlling method using the same.

以往為了防除有害生物而合成種種的化合物(參照非專利文獻1、2)。而且，在專利文獻1、2及3揭示有某種酯化合物。但是，該等揭示的有害生物防除成分的防除效力未必令人滿意。Conventionally, various compounds have been synthesized in order to prevent pests (see Non-Patent Documents 1 and 2). Further, Patent Documents 1, 2 and 3 disclose certain ester compounds. However, the control efficacy of the disclosed pest control ingredients is not necessarily satisfactory.

[專利文獻1]：日本國特開昭57-165343號公報 [專利文獻2]：日本國特許第4289331號公報 [專利文獻3]：日本國特許第2647411號公報[Patent Document 1] Japanese Patent Publication No. 4,287,331 [Patent Document 3]: Japanese Patent No. 2647741

[非專利文獻1]：[續醫藥品的開發 第18卷 農藥的開發III]、廣川書店、1993年、p.493 [非專利文獻2]：[擬除蟲菊酯(pyrethroid)]、Springe公司、2012年[Non-Patent Document 1]: [Development of Pharmaceutical Products, Volume 18, Development of Pesticides III], Hirokawa Bookstore, 1993, p. 493 [Non-Patent Document 2]: [pyrethroid], Springe Company, 2012

本發明是以提供具有優良的有害生物防除效力的新穎酯化合物及使用該酯化合物的害蟲的驅除方法為課題。The present invention has been made in an effort to provide a novel ester compound having excellent pest control efficacy and a method for repelling pests using the ester compound.

本發明人們考慮了可藉由將拜富寧(transfluthrin)、美特寧(metofluthrin)及丙氟菊酯(profluthrin)所代表的四氟苄基酯(tetrafluorobenzyl ester)化合物的芳香環上的F原子取代成Cl原子或Br原子而開創具有殘餘效應(residual effect)的提高等優良的特性之化合物。專心致志進行了檢討的結果發現，以下列通式(1)表示的酯化合物(以下有稱為含Cl酯化合物的情形)，或以下列通式(I)表示的酯化合物(以下有稱為含Br酯化合物的情形)具有優良的有害生物防除效力，而達到完成本發明。The present inventors have considered an F atom on an aromatic ring which can be represented by a tetrafluorobenzyl ester compound represented by transfluthrin, metofluthrin and profluthrin. Substituting into a Cl atom or a Br atom creates a compound having excellent characteristics such as an improvement in a residual effect. As a result of the review, it was found that the ester compound represented by the following general formula (1) (hereinafter referred to as a Cl-containing ester-containing compound) or the ester compound represented by the following general formula (I) (hereinafter referred to as In the case of the Br ester compound, it has an excellent pest control effect, and the completion of the present invention is achieved.

也就是說，本發明是關於以下的發明。 [1]、一種酯化合物，以下列的通式[化1](1)表示：That is, the present invention relates to the following invention. [1] An ester compound represented by the following formula [Chemical Formula 1] (1):

[化1][式中R1 是表示氫原子或甲基，R1 表示甲基時R2 也表示甲基，而且R1 表示氫原子時R2 為以下列通式[化2](2)[Chemical 1] Wherein R 1 represents a hydrogen atom or a methyl group, R 1 represents a methyl group, and R 2 also represents a methyl group, and when R 1 represents a hydrogen atom, R 2 is represented by the following formula [2] (2)

[化2](此處X及Y為同一或不同，表示氫原子、鹵素原子、氰基、碳數1~4的烷基、碳數2~5的烷氧基羰基(alkoxy carbonyl group)或碳數1~4的鹵烷基(haloalkyl))表示的基，R3 是表示氫原子、三氟甲基(trifluoromethyl)、甲基、甲氧基、甲氧基甲基、烯丙基、乙炔基或丙炔基]。 [2]、一種酯化合物，以下列的通式[化3](I)表示：[Chemical 2] (wherein X and Y are the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy carbonyl group having 2 to 5 carbon atoms, or a carbon number of 1~) a group represented by a haloalkyl group, and R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propyne group. base]. [2] An ester compound represented by the following formula [Chemical Formula 3] (I):

[化3][式中R1 是表示氫原子或甲基，R1 表示甲基時R2 也表示甲基，而且R1 表示氫原子時R2 為以下列通式[化4](II)[Chemical 3] Wherein R 1 represents a hydrogen atom or a methyl group, R 1 represents a methyl group, and R 2 also represents a methyl group, and when R 1 represents a hydrogen atom, R 2 is in the following formula [Chemical Formula 4] (II)

[化4](此處X及Y為同一或不同，表示氫原子、鹵素原子、氰基、碳數1~4的烷基、碳數2~5的烷氧基羰基或碳數1~5的鹵烷基)表示的基，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]。 [3]、如[1]或[2]之酯化合物，其中R3 是以氫原子表示。 [4]、如[1]或[2]之酯化合物，其中R3 是以甲基表示。 [5]、如[1]或[2]之酯化合物，其中R3 是以甲氧基甲基表示。 [6]、如[1]之酯化合物，其中R3 是以乙炔基表示。 [7]、一種有害生物防除劑，含有以[1]至[6]中任一項的酯化合物作為有效成分。 [8]、一種有害生物的防除方法，將[1]至[6]中任一項的酯化合物施用於有害生物或有害生物的棲息地。[Chemical 4] (wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. Wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propynyl group. [3] The ester compound according to [1] or [2], wherein R 3 is represented by a hydrogen atom. [4] The ester compound according to [1] or [2], wherein R 3 is represented by a methyl group. [5] The ester compound according to [1] or [2], wherein R 3 is represented by a methoxymethyl group. [6] The ester compound according to [1], wherein R 3 is represented by an ethynyl group. [7] A pest control agent comprising the ester compound according to any one of [1] to [6] as an active ingredient. [8] A method for controlling a pest, which comprises applying the ester compound according to any one of [1] to [6] to a habitat of a pest or a pest.

本發明化合物因具有優良的有害生物防除效力，故作為有害生物防除劑的有效成分有用。The compound of the present invention is useful as an active ingredient of a pest control agent because it has excellent pest control efficacy.

在本發明化合物有R1 表示氫原子時，存在如下的情形：自存在於環丙烷環上的1位及3位的兩個不對稱碳(asymmetric carbon)原子衍生的光學異構物(optical isomer)，及自存在於環丙烷環3位的取代基的1’位的雙鍵衍生的異構物的情形，在本發明包含有具有有害生物防除活性的各異構物及任意的比率的異構物混合物。In the case where the compound of the present invention has R 1 represents a hydrogen atom, there are cases in which an optical isomer derived from two asymmetric carbon atoms present at the 1- and 3-positions on the cyclopropane ring (optical isomer) And, in the case of an isomer derived from a double bond at the 1' position of the substituent at the 3-position of the cyclopropane ring, the present invention contains the respective isomers having pesticidal activity and an arbitrary ratio Structure mixture.

＜含Cl酯化合物的製造法＞ 就本發明化合物(含Cl酯化合物)的製造法進行說明。 本發明化合物若是製造通常的酯化合物的方法，則未被特別限定，惟例如可藉由以下所示的方法製造。<Method for Producing Cl-Containing Compound> A method for producing the compound (including a Cl ester-containing compound) of the present invention will be described. The compound of the present invention is not particularly limited as long as it is a method for producing a usual ester compound, and can be produced, for example, by the method shown below.

(參考製造法1) 藉由使以下列的式[化5](3)：(Refer to Manufacturing Method 1) by making the following formula [5] (3):

[化5]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)：[Chemical 5] An alcohol compound (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propynyl group), and the following formula [ 6] (4):

[化6][式中R1 是表示氫原子或甲基，R1 表示甲基時R2 也表示甲基，而且R1 表示氫原子時R2 為以下列通式[化7](2)[Chemical 6] Wherein R 1 represents a hydrogen atom or a methyl group, R 1 represents a methyl group, and R 2 also represents a methyl group, and when R 1 represents a hydrogen atom, R 2 is represented by the following formula [7] (2)

[化7](此處X及Y為同一或不同，表示氫原子、鹵素原子、氰基、碳數1~4的烷基、碳數2~5的烷氧基羰基或碳數1~4的鹵烷基)表示的基]表示的羧酸化合物或其反應性衍生物反應得到本發明化合物。[Chemistry 7] (wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms. The carboxylic acid compound represented by the group represented by the formula or a reactive derivative thereof is reacted to obtain a compound of the present invention.

作為該反應性衍生物可舉出：以式(4)表示的羧酸化合物的酸鹵化物(acid halide)、該羧酸化合物的酸酐及該羧酸化合物的酯等。作為該酸鹵化物可舉出酸性氯化物(acid chloride)化合物，作為酯可舉出甲酯、乙酯等。 該反應通常在縮合劑或鹼的存在下在溶劑中進行。 作為縮合劑例如可舉出：二環己碳二亞胺(dicyclohexylcarbodiimide)、1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride)。而且，作為鹼可舉出：三乙胺(triethylamine)、吡啶(pyridine)、4-二甲胺基吡啶(4-dimethylaminopyridine)、二異丙基乙胺(diisopropylethylamine)等的有機鹼。 作為溶劑例如可舉出：甲苯及己烷等的烴；四氫呋喃(tetrahydrofuran)等的醚；乙酸乙酯(ethyl acetate)等的酯以及氯苯(chlorobenzene)等的鹵化烴及該等的混合溶劑等。Examples of the reactive derivative include an acid halide of a carboxylic acid compound represented by the formula (4), an acid anhydride of the carboxylic acid compound, and an ester of the carboxylic acid compound. An acid chloride compound is mentioned as this acid halide, and a methyl ester, an ethyl ester, etc. are mentioned as an 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). Further, 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. .

在該反應中，以式(3)表示的醇化合物與以式(4)表示的羧酸化合物或其反應性衍生物之使用莫耳比可任意設定，較佳為等莫耳或接近其之比例。 縮合劑或鹼相對於1莫耳以式(3)表示的醇化合物，通常能以0.25莫耳到過量任意的比例使用，較佳為0.5莫耳~2莫耳。該等縮合劑或鹼係依照以式(4)表示的羧酸化合物或其反應性衍生物的種類適宜選擇。 反應結束後的反應混合物可藉由將其過濾並將濾液濃縮，或者將水注加到反應混合物後施以有機溶劑萃取、濃縮等的通常的後處理操作，得到本發明化合物。所得到的本發明化合物可藉由層析法(chromatography)、蒸餾等的操作而精製。In the reaction, the molar ratio of the alcohol compound represented by the formula (3) to the carboxylic acid compound represented by the formula (4) or a reactive derivative thereof may be arbitrarily set, preferably in the form of or in the vicinity of the molar ratio. proportion. The condensing agent or base can be used in an arbitrary ratio of from 0.25 mol to the excess, preferably from 0.5 mol to 2 mol, based on 1 mol of the alcohol compound represented by the formula (3). These condensing agents or bases are appropriately selected depending on the type of the carboxylic acid compound represented by the formula (4) or a reactive derivative thereof. The reaction mixture after completion of the reaction can be obtained by filtering it and concentrating the filtrate, or by adding a water to the reaction mixture, followed by a usual post-treatment operation of extracting, concentrating, or the like with an organic solvent to obtain a compound of the present invention. The obtained compound of the present invention can be purified by an operation such as chromatography or distillation.

(參考製造法2) 在上述參考製造法1中以式(3)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)可藉由例如下列合成路徑(synthetic pathway)[化8](5)→(3)製造：(Reference Production Method 2) The alcohol compound represented by the formula (3) in the above Reference Production Method 1 (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, Allyl, ethynyl or propynyl) can be produced, for example, by the following synthetic pathway [5] (5) → (3):

[化8]也就是說，可藉由在不活性溶劑(例如己烷、甲苯、四氫呋喃、***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。[化8] That is, the ester compound (5) can be obtained by using an inactive solvent (e.g., hexane, toluene, tetrahydrofuran, diethyl ether, etc.) (wherein R is an alkyl group having a carbon number of 1 to 4, and R 3 is represented by a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propynyl group) and a reducing agent (for example, lithium aluminum hydride, diisobutyl) Aluminium hydride (diisobutylaluminium hydride) or the like is produced by reacting at -30 to 20 ° C for 1 to 10 hours.

(參考製造法3) 在上述參考製造法2中以式(5)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)可藉由例如下列合成路徑[化9](6)→(5)製造：(Reference Production Method 3) The ester compound represented by the formula (5) in the above Reference Production Method 2 (wherein R is an alkyl group having a carbon number of 1 to 4, and R 3 is a hydrogen atom, a trifluoromethyl group, or a The base, methoxy, methoxymethyl, allyl, ethynyl or propynyl can be produced, for example, by the following synthetic route [9] (6) → (5):

[化9]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。[Chemistry 9] That is, it can be produced by chlorinating the ester compound (6) by a Sandmeyer reaction. Specifically, the diazonium salt intermediate can be prepared by slowly adding an aqueous solution of sodium nitrite in 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. Here, copper chloride (I) (cuprous chloride) is added and divided, and it is produced by reacting at 20 to 60 ° C for 1 to 10 hours.

(參考製造法4) 在上述參考製造法3中以式(6)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)可藉由例如下列合成路徑[化10](7)→(6)製造：(Reference Production Method 4) The ester compound represented by the formula (6) in the above Reference Production Method 3 (wherein R is an alkyl group having a carbon number of 1 to 4, and R 3 is a hydrogen atom, a trifluoromethyl group, or a The base, methoxy, methoxymethyl, allyl, ethynyl or propynyl group can be produced, for example, by the following synthetic route [10] (7) → (6):

[化10]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、***、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。[化10] That is, it can be used in a metal catalyst (for example, palladium carbon, platinum, rhodium, ruthenium, etc.) in an organic solvent (for example, ethyl acetate, hexane, toluene, tetrahydrofuran, diethyl ether, an alcohol having 1 to 3 carbon atoms, etc.). The ester compound (7) is reacted in a hydrogen atmosphere at 10 to 30 ° C for 1 to 10 hours in the presence of hydrogen.

(參考製造法5) 在上述參考製造法4中以式(7)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)可藉由例如下列合成路徑[化11](8)→(7)製造：(Reference Production Method 5) The ester compound represented by the formula (7) in the above Reference Production Method 4 (wherein R is an alkyl group having a carbon number of 1 to 4, and R 3 is a hydrogen atom, a trifluoromethyl group, or a The base, methoxy, methoxymethyl, allyl, ethynyl or propynyl group can be produced, for example, by the following synthetic route [11] (8) → (7):

[化11]也就是說，可藉由在不活性溶劑(例如己烷、甲苯、四氫呋喃、***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。[11] That is, the ester compound (8) can be reacted with an ester (8) in the presence of a base (e.g., triethylamine, ethyldiisopropylamine) in an inert solvent (e.g., hexane, toluene, tetrahydrofuran, diethyl ether, etc.). Benzylamine is produced by reacting at 60 to 100 ° C for 5 to 15 hours.

另一方面，以式(4)表示的羧酸化合物或其反應性衍生物為眾所周知物質。On the other hand, the carboxylic acid compound represented by the formula (4) or a reactive derivative thereof is a well-known substance.

作為本發明化合物例如可舉出如以下的化合物。 本發明化合物A1；2-氯-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物B1；2-氯-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物C1；2-氯-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物D1；2-氯-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物E1；2-氯-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物F1；2-氯-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物G1；2-氯-3,5,6-三氟苄基 (1RS)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物H1；2-氯-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物I1；2-氯-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物J1；2-氯-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物K1；2-氯-3,5,6-三氟苄基 (1R)-順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物L1；2-氯-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物M1；2-氯-3,5,6-三氟苄基 (1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物N1；2-氯-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物O1；2-氯-3,5,6-三氟苄基 (1R)-反式,順式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物(isomer)的比率：Z/E=約8/1)、 本發明化合物P1；2-氯-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物Q1；2-氯-3,5,6-三氟苄基 (1R)-反式,順式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物R1；2-氯-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物S1；2-氯-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物T1；2-氯-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物U1；2-氯-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-氰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物V1；2-氯-3,5,6-三氟苄基 (1R)-反式-3-[(Z)-(2-氰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物W1；2-氯-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯、 本發明化合物A2；2-氯-4-甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物B2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物C2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物D2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物E2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物F2；2-氯-4-甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物G2；2-氯-4-甲基-3,5,6-三氟苄基 (1RS)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物H2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物I2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物J2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物K2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物L2；2-氯-4-甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物M2；2-氯-4-甲基-3,5,6-三氟苄基 (1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物N2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物O2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物P2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物Q2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物R2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物S2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物T2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物U2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-氰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物V2；2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-[(Z)-(2-氰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物W2；2-氯-4-甲基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯、 本發明化合物A3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物B3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物C3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物D3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物E3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物F3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物G3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物H3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物I3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物J3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物K3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物L3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物M3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物N3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物O3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物P3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物Q3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物R3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物S3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物T3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物U3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-氰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物V3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-[(Z)-(2-氰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物W3；2-氯-4-甲氧基甲基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯、 本發明化合物A4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物B4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物C4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物D4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物E4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物F4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物G4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1RS)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物H4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物I4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物J4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物K4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物L4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物M4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物N4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物O4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式,順式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物P4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物Q4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物R4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物S4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物T4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物U4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-氰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物V4；2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-[(Z)-(2-氰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物W4；2-氯-4-乙炔基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯、 本發明化合物A5；2-氯-3,5,6-三氟-4-三氟甲基苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物B5；4-烯丙基-2-氯-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物C5；2-氯-4-丙炔基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物D5；2-氯-4-甲氧基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯。Examples of the compound of the present invention include the following compounds. The present invention A1; 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-dimethylcyclopropanecarboxylate, the compound of the invention C1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate, the compound of the invention D1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2 -difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound E1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3 -(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound F1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1RS) -trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound G1 of the invention; 2-chloro-3,5,6 -trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention H1; 2-chloro- 3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate Ester, the compound of the invention I1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethyl Cyclopropane carboxylate, compound J1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl -2,2-dimethylcyclopropanecarboxylate, compound K1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-cis-3-(2,2-dibromo) 1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention L1; 2-chloro-3,5,6-trifluorobenzyl (1RS)-trans, cis-3 -(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention M1; 2-chloro-3,5,6-tri Fluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate, Ben Inventive compound N1; 2-chloro-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl] -2,2-dimethylcyclopropanecarboxylate, compound O1 of the invention; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(1-propenyl) -2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), compound P1 of the present invention; 2-chloro-3,5 , 6-three Fluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1 ), a compound of the invention Q1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl) ]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention R1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2 -methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the present compound S1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans , cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, the compound T1 of the invention; 2-chloro-3,5 ,6-trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, the invention Compound U1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-cyano-1-propenyl)]-2,2 - dimethylcyclopropanecarboxylate, the compound of the invention V1; 2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3-[(Z)-(2-cyano-1 -propenyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention W1; 2-chloro-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclo Propane carboxy Ester, compound A2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1-propenyl)- 2,2-dimethylcyclopropanecarboxylate, compound B2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-( 2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention C2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R -trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention D2; 2-chloro-4-methyl-3,5, 6-trifluorobenzyl (1R)-trans, cis-3-(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound E2 of the invention; 2-Chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-difluoro-1-vinyl)-2,2-dimethyl ring Propane 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-dimethylcyclopropanecarboxylate, compound G2 of the invention; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1RS)-trans-3 -(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention H2; 2-chloro-4-methyl-3,5,6-tri Benzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound I2 of the invention; 2-chloro- 4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate , the compound of the invention J2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl) -2,2-dimethylcyclopropanecarboxylate, the compound of the invention K2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-cis-3-(2, 2-Dibromo-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention L2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1RS )-trans, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, compound M2; Chloro-4-methyl-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]- 2,2-Dimethylcyclopropanecarboxylate, the compound of the invention N2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z) -2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate, the compound O2 of the invention; 2-chloro-4-methyl-3,5 ,6-trifluorobenzyl (1R)-trans, cis-3 -(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), the compound of the invention P2; 2-chloro- 4-Methyl-3,5,6-trifluorobenzyl(1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (on isomerization of double bonds) Ratio of the product: Z/E = about 8/1), the compound of the present invention Q2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3- [(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention R2; 2-chloro-4-methyl-3,5, 6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, a compound of the invention S2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl) ]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention T2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-cis-3-[( Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, the compound U2 of the invention; 2-chloro-4-methyl-3,5,6- Trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-cyano-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, invented V2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(Z)-(2-cyano-1-propenyl)]-2 ,2-dimethylcyclopropanecarboxylate, the compound of the invention W2; 2-chloro-4-methyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate Acid ester, compound A3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1- Propenyl)-2,2-dimethylcyclopropanecarboxylate, compound B3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans , cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention C3; 2-chloro-4-methoxymethyl-3, 5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, compound D3 of the invention; 2-chloro 4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-difluoro-1-vinyl)-2,2-di Methylcyclopropanecarboxylate, the compound of the invention E3; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-di Fluor-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound F3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl ( 1RS)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound G3 of the invention; 2-chloro-4-methyl Oxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane Carboxylic ester, compound H3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1- Vinyl)-2,2-dimethylcyclopropanecarboxylate, compound I3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans 3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound J3 of the invention; 2-chloro-4-methoxymethyl-3,5 ,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound K3 of the invention ; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-cis-3-(2,2-dibromo-1-vinyl)-2,2- Dimethylcyclopropanecarboxylate, the compound of the invention L3; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2 -Chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, compound M3 of the invention; 2-chloro-4-methoxymethyl-3 ,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclo Propane carboxylate, compound N3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-2-chloro- 3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate, the compound O3 of the invention; 2-chloro-4-methoxymethyl-3,5,6 -trifluorobenzyl (1R)-trans, cis-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio for isomers of double bonds: Z/E = about 8/1), the compound of the invention P3; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)- 2,2-Dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), compound Q3 of the present invention; 2-chloro-4-methoxymethyl- 3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane Carboxylic ester, compound R3 of the invention; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxy Carbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the present compound S3; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl ( 1R)-reverse , cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, the compound T3 of the invention; 2-chloro-4-methyl Oxymethyl-3,5,6-trifluorobenzyl(1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethyl Cyclopropanecarboxylate, the compound of the invention U3; 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)- (2-Cyano-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention V3; 2-chloro-4-methoxymethyl-3,5,6-tri Fluorobenzyl (1R)-trans-3-[(Z)-(2-cyano-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention W3; Chloro-4-methoxymethyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, compound A4 of the invention; 2-chloro-4-ethynyl -3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, the invention Compound B4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2,2- Dimethylcyclopropanecarboxylate, the compound of the invention C4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1- C Alkenyl)-2,2-dimethylcyclopropanecarboxylate, compound D4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis 3-(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound E4 of the invention; 2-chloro-4-ethynyl-3,5,6- Trifluorobenzyl (1R)-trans-3-(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound F4 of the invention; 2-chloro-4 -ethynyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate Acid ester, compound G4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)- 2,2-Dimethylcyclopropanecarboxylate, the compound of the invention H4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-( 2,2-Dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound I4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention J4; 2-chloro-4-ethynyl- 3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropane Acid ester, compound K4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-cis-3-(2,2-dibromo-1-vinyl)- 2,2-Dimethylcyclopropanecarboxylate, the compound of the invention L4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-( 2-Chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention M4; 2-chloro-4-ethynyl-3,5, 6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylic acid Ester, the compound of the invention N4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-2-chloro-3,3,3- Trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate, compound O4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)- Trans, cis-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), the present invention Compound P4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Ratio of isomers of 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-dimethylcyclopropanecarboxylate, the compound of the invention R4; 2-chloro 4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethyl Base cyclopropane carboxylate, compound S4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2 -methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention T4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl ( 1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, the compound U4 of the invention; 2-chloro-4 -ethynyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-cyano-1-propenyl)]-2,2-dimethyl Base cyclopropane carboxylate, compound V4 of the invention; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl (1R)-trans-3-[(Z)-(2-cyano) 1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention W4; 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl 2,2,3 , 3-tetramethylcyclopropanecarboxylate, the compound A5 of the invention; 2-chloro-3,5,6-trifluoro-4-trifluoromethylbenzyl (1R)-trans-3-(2, 2-dichloro-1- Vinyl)-2,2-dimethylcyclopropanecarboxylate, compound B5 of the invention; 4-allyl-2-chloro-3,5,6-trifluorobenzyl (1R)-trans-3 -(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: 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-dimethylcyclopropanecarboxylic acid Ester, the compound of the invention D5; 2-chloro-4-methoxy-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2, 2-Dimethylcyclopropanecarboxylate.

＜含Br酯化合物的製造法＞ 就本發明化合物(含Br酯化合物)的製造法進行說明。 本發明化合物若是製造通常的酯化合物的方法，則未被特別限定，惟例如可藉由以下所示的方法製造。<Method for Producing Br-Containing Compound> A method for producing the compound (Br-containing compound) of the present invention will be described. The compound of the present invention is not particularly limited as long as it is a method for producing a usual ester compound, and can be produced, for example, by the method shown below.

(參考製造法1) 藉由使以下列的式[化12](III)：(Refer to Manufacturing Method 1) by making the following formula [Chem. 12] (III):

[化12]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)：[化12] An alcohol compound (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propynyl group), and the following formula [ 13] (IV):

[化13][式中R1 是表示氫原子或甲基，R1 表示甲基時R2 也表示甲基，而且R1 表示氫原子時R2 為以下列通式[化14](V)[Chemistry 13] Wherein R 1 represents a hydrogen atom or a methyl group, R 1 represents a methyl group, and R 2 also represents a methyl group, and when R 1 represents a hydrogen atom, R 2 is represented by the following formula [Chem. 14] (V)

[化14](此處X及Y為同一或不同，表示氫原子、鹵素原子、氰基、碳數1~4的烷基、碳數2~5的烷氧基羰基或碳數1~5的鹵烷基)表示的基]表示的羧酸化合物或其反應性衍生物反應得到本發明化合物。[Chemistry 14] (wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. The carboxylic acid compound represented by the group represented by the formula or a reactive derivative thereof is reacted to obtain a compound of the present invention.

作為該反應性衍生物可舉出：以式(IV)表示的羧酸化合物的酸鹵化物、該羧酸化合物的酸酐及該羧酸化合物的酯等。作為該酸鹵化物可舉出酸性氯化物化合物，作為酯可舉出甲酯、乙酯等。 該反應通常在縮合劑或鹼的存在下在溶劑中進行。 作為縮合劑例如可舉出：二環己碳二亞胺、1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽。而且，作為鹼可舉出：三乙胺、吡啶、4-二甲胺基吡啶、二異丙基乙胺等的有機鹼。 作為溶劑例如可舉出：甲苯及己烷等的烴；四氫呋喃等的醚；乙酸乙酯等的酯以及氯苯等的鹵化烴及該等的混合溶劑等。Examples of the reactive derivative include an acid halide of a carboxylic acid compound represented by the formula (IV), an acid anhydride of the carboxylic acid compound, and an ester of the carboxylic acid compound. The acid halide is exemplified by an acid chloride compound, and examples of the ester include a methyl ester and an 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. Further, examples of the base include organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine, and diisopropylethylamine. Examples of the solvent include a hydrocarbon such as toluene or hexane; an ether such as tetrahydrofuran; an ester such as ethyl acetate; a halogenated hydrocarbon such as chlorobenzene; and a mixed solvent thereof.

在該反應中，以式(III)表示的醇化合物與以式(IV)表示的羧酸化合物或其反應性衍生物之使用莫耳比可任意設定，較佳為等莫耳或接近其之比例。 縮合劑或鹼相對於1莫耳以通式(III)表示的醇化合物，通常能以0.25莫耳到過量任意的比例使用，較佳為0.5莫耳~2莫耳。該等縮合劑或鹼係依照以通式(IV)表示的羧酸化合物或其反應性衍生物的種類適宜選擇。 反應結束後的反應混合物可藉由將其過濾並將濾液濃縮，或者將水注加到反應混合物後施以有機溶劑萃取、濃縮等的通常的後處理操作，得到本發明化合物。所得到的本發明化合物可藉由層析法、蒸餾等的操作而精製。In the reaction, the molar ratio of the alcohol compound represented by the formula (III) to the carboxylic acid compound represented by the formula (IV) or a reactive derivative thereof may be arbitrarily set, preferably in the vicinity of or in the vicinity of the molar ratio. proportion. The condensing agent or base is usually used in an amount of from 0.25 mol to the excess, preferably from 0.5 mol to 2 mol, based on 1 mol of the alcohol compound represented by the formula (III). These condensing agents or bases are appropriately selected depending on the type of the carboxylic acid compound represented by the formula (IV) or a reactive derivative thereof. The reaction mixture after completion of the reaction can be obtained by filtering it and concentrating the filtrate, or by adding a water to the reaction mixture, followed by a usual post-treatment operation of extracting, concentrating, or the like with an organic solvent to obtain a compound of the present invention. The obtained compound of the present invention can be purified by an operation such as chromatography, distillation or the like.

(參考製造法2) 在上述參考製造法1中以通式(III)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)可藉由例如下列合成路徑[化15](VI)→(III)製造：(Reference Production Method 2) The alcohol compound represented by the formula (III) in the above Reference Production Method 1 (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, or a methoxymethyl group) , allyl, ethynyl or propynyl) can be produced, for example, by the following synthetic route [Chem. 15] (VI) → (III):

[化15]也就是說，可藉由在不活性溶劑(例如己烷、甲苯、四氫呋喃、***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。[化15] That is, an ester compound represented by the formula (VI) can be obtained by using an alkyl group represented by the formula (VI) in an inert solvent (for example, hexane, toluene, tetrahydrofuran, diethyl ether, etc.) (wherein R is an alkyl group having a carbon number of 1 to 4) , R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propynyl group) and a reducing agent (for example, lithium aluminum hydride, diisobutylene) Aluminum hydride or the like is produced by reacting at -30 to 20 ° C for 1 to 10 hours.

(參考製造法3) 在上述參考製造法2中以通式(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)可藉由例如下列合成路徑[化16](VII)→(VI)製造：(Reference Production Method 3) The ester compound represented by the formula (VI) in the above Reference Production Method 2 (wherein R is an alkyl group having 1 to 4 carbon atoms, and R 3 is a hydrogen atom or a trifluoromethyl group; Methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl can be produced, for example, by the following synthetic route [Chem. 16] (VII) → (VI):

[化16]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。[Chemistry 16] That is, by the ester compound represented by the formula (VII) (wherein R is an alkyl group having a carbon number of 1 to 4, and R 3 is a hydrogen atom, a trifluoromethyl group, a methyl group or a methoxy group). The base, methoxymethyl, allyl, ethynyl or propynyl group is produced by bromination by a Sandmeyer reaction. Specifically, the tetrabutylammonium bromide, camphorsulfonic acid, sodium nitrite, and divalent copper bromide may be sequentially added to the ester compound represented by the general formula (VII) at room temperature. (wherein R is an alkyl group having 1 to 4 carbon atoms; and R 3 is a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propynyl group; The acetonitrile solution was produced by reacting it at 20 to 60 ° C for 1 to 48 hours.

(參考製造法4) 在上述參考製造法3中以通式(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)可藉由例如下列合成路徑[化17](VIII)→(VII)製造：(Reference Production Method 4) The ester compound represented by the formula (VII) in the above Reference Production Method 3 (wherein R is an alkyl group having 1 to 4 carbon atoms, and R 3 is a hydrogen atom or a trifluoromethyl group; Methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl can be produced, for example, by the following synthetic route [Chem. 17] (VIII) → (VII):

[化17]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、***、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。[化17] That is, it can be used in a metal catalyst (for example, palladium carbon, platinum, rhodium, ruthenium, etc.) in an organic solvent (for example, ethyl acetate, hexane, toluene, tetrahydrofuran, diethyl ether, an alcohol having 1 to 3 carbon atoms, etc.). An ester compound represented by the formula (VIII) in a hydrogen atmosphere at 10 to 30 ° C (wherein R is an alkyl group having 1 to 4 carbon atoms, and R 3 is a hydrogen atom or a trifluoromethyl group; Methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl) is produced by reacting for 1 to 10 hours.

(參考製造法5) 在上述參考製造法4中以通式(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)可藉由例如下列合成路徑[化18](IX)→(VIII)製造：(Reference Production Method 5) The ester compound represented by the formula (VIII) in the above Reference Production Method 4 (wherein R is an alkyl group having 1 to 4 carbon atoms, and R 3 is a hydrogen atom or a trifluoromethyl group; Methyl, methoxy, methoxymethyl, allyl, ethynyl or propynyl can be produced, for example, by the following synthetic route [Chem. 18] (IX) → (VIII):

[化18]也就是說，可藉由在不活性溶劑(例如己烷、甲苯、四氫呋喃、***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。[化18] That is, the ester represented by the formula (IX) can be obtained by the presence of a base (for example, triethylamine, ethyldiisopropylamine) in an inert solvent (for example, hexane, toluene, tetrahydrofuran, diethyl ether, etc.). a compound (wherein R represents an alkyl group having 1 to 4 carbon atoms, and R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propyne group) The base is produced by reacting with benzylamine at 60 to 100 ° C for 5 to 15 hours.

另一方面，以通式(IV)表示的羧酸化合物或其反應性衍生物為眾所周知物質。On the other hand, the carboxylic acid compound represented by the formula (IV) or a reactive derivative thereof is a well-known substance.

作為本發明化合物例如可舉出如以下的化合物。 本發明化合物1；2-溴-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物2；2-溴-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物3；2-溴-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物4；2-溴-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物5；2-溴-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物6；2-溴-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物7；2-溴-3,5,6-三氟苄基 (1RS)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物8；2-溴-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物9；2-溴-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物10；2-溴-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物11；2-溴-3,5,6-三氟苄基 (1R)-順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物12；2-溴-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物13；2-溴-3,5,6-三氟苄基 (1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物14；2-溴-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物15；2-溴-3,5,6-三氟苄基 (1R)-反式,順式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物(isomer)的比率：Z/E=約8/1)、 本發明化合物16；2-溴-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物17；2-溴-3,5,6-三氟苄基 (1R)-反式,順式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物18；2-溴-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物19；2-溴-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物20；2-溴-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物21；2-溴-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-氰基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約2/1)、 本發明化合物22；2-溴-3,5,6-三氟苄基 (1R)-反式-3-(2-氰基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約2/1)、 本發明化合物23；2-溴-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯、 本發明化合物24；2-溴-4-甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物25；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物26；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物27；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物28；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物29；2-溴-4-甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物30；2-溴-4-甲基-3,5,6-三氟苄基 (1RS)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物31；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物32；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物33；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物34；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物35；2-溴-4-甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物36；2-溴-4-甲基-3,5,6-三氟苄基 (1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物37；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物38；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物39；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物40；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物41；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物42；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物43；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物44；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-氰基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約2/1)、 本發明化合物45；2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-氰基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約2/1)、 本發明化合物46；2-溴-4-甲基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯、 本發明化合物47；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物48；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物49；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物50；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物51；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氟-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物52；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物53；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物54；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物55；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物56；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物57；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-順式-3-(2,2-二溴-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物58；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-反式,順式-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物59；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物60；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯、 本發明化合物61；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物62；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物63；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物64；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物65；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物66；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯、 本發明化合物67；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式,順式-3-(2-氰基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約2/1)、 本發明化合物68；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-氰基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約2/1)、 本發明化合物69；2-溴-4-甲氧基甲基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯、 本發明化合物70；2-溴-3,5,6-三氟-4-三氟甲基苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物71；4-烯丙基-2-溴-3,5,6-三氟苄基　(1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物72；4-烯丙基-2-溴-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(關於雙鍵的異構物的比率：Z/E=約8/1)、 本發明化合物73；2-溴-4-丙炔基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯、 本發明化合物74；2-溴-4-甲氧基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯、Examples of the compound of the present invention include the following compounds. Compound 1 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethyl Cyclopropanecarboxylate, compound 2 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2 ,2-dimethylcyclopropanecarboxylate, compound 3 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate, compound 4 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2 -difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 5 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3 -(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 6 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1RS) -trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 7 of the invention; 2-bromo-3,5,6 -trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 8 of the invention; 2-bromo- 3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, The present invention is a compound 9; 2-bromo-3,5,6-trifluorobenzyl(1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclo Propane carboxylate, compound 10 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl)- 2,2-Dimethylcyclopropanecarboxylate, compound 11 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-cis-3-(2,2-dibromo-1 -vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 12 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-( 2-Chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, compound 13 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate, a compound of the invention 14; 2-bromo-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2 ,2-dimethylcyclopropanecarboxylate, compound 15 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(1-propenyl)- 2,2-Dimethylcyclopropanecarboxylate (ratio of isomers for double bonds: Z/E = about 8/1), compound 16 of the invention; 2-bromo-3,5,6 -trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers of double bonds: Z/E = about 8/1), Inventive compound 17; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2 ,2-dimethylcyclopropanecarboxylate, the compound of the invention 18; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxy Carbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, compound 19 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis -3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, compound 20 of the invention; 2-bromo-3,5,6- Trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, compound 21 of the invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Ratio of isomers of double bonds: Z/E = about 2/1), Compound 22 of the present invention; 2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-( 2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers of double bonds: Z/E = about 2/1), Inventive compound 23; 2-bromo-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, compound 24 of the invention; 2-bromo-4-methyl-3 ,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, compound 25 of the invention ; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethyl Cyclopropane carboxylate, compound 26 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate, compound 27 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3 -(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention 28; 2-bromo-4-methyl-3,5,6-trifluoro Benzyl (1R)-trans-3-(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 29 of the invention; 2-bromo-4-methyl 3-,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate a compound of the invention 30; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1RS)-trans-3-(2,2-dichloro-1-vinyl)-2, 2-two Base cyclopropane carboxylate, compound 31 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro 1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 32 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans 3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention 33; 2-bromo-4-methyl-3,5,6- Trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 34 of the invention; Bromo-4-methyl-3,5,6-trifluorobenzyl(1R)-cis-3-(2,2-dibromo-1-ethenyl)-2,2-dimethylcyclopropanecarboxylate Acid ester, compound 35 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2-chloro-3,3,3- Trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, compound 36 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1RS)- Cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate, compound 37 of the invention; 2-bromo 4-methyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2 ,2-dimethylcyclopropanecarboxylate, Inventive compound 38; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(1-propenyl)-2,2-dimethyl ring Propane carboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), compound 39 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl ( 1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), the present invention Compound 40; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl) ]]-2,2-dimethylcyclopropanecarboxylate, compound 41 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-[ (E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the compound 42 of the invention; 2-bromo-4-methyl-3,5,6 -trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, Inventive compound 43; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)] -2,2-dimethylcyclopropanecarboxylate, compound 44 of the invention; 2-bromo-4-methyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3- (2- Cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers for double bonds: Z/E = about 2/1), compound 45 of the invention; 2-bromo 4-methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylate ( Regarding the ratio of the isomer of the double bond: Z/E = about 2/1), the compound of the invention 46; 2-bromo-4-methyl-3,5,6-trifluorobenzyl 2,2,3, 3-tetramethylcyclopropanecarboxylate, the compound of the invention 47; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3- (2-Methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, the compound of the invention 48; 2-bromo-4-methoxymethyl-3,5,6-trifluoro Benzyl (1R)-trans, cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, compound 49 of the invention; 2-bromo-4- Methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, The present invention 50; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-difluoro-1-ethene -2,2-dimethylcyclopropanecarboxylate, compound 51 of the invention; 2-bromo-4-methoxymethyl-3 5,6-trifluorobenzyl (1R)-trans-3-(2,2-difluoro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 52 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans, cis-3-(2,2-dichloro-1-vinyl)-2, 2-Dimethylcyclopropanecarboxylate, compound 53 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-trans-3-(2, 2-Dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 54 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 55 of the invention; 2-bromo-4 -methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate Acid ester, compound 56 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(2,2-dibromo- 1-vinyl)-2,2-dimethylcyclopropanecarboxylate, compound 57 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)- Cis-3-(2,2-dibromo-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, 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-dimethyl Cyclopropanecarboxylate, the compound of the invention 59; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro -3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate, compound 60 of the invention; 2-bromo-4-methoxymethyl-3,5, 6-trifluorobenzyl (1R)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylic acid Ester, compound 61 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-(1-propenyl)-2, 2-Dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), compound 62 of the invention; 2-bromo-4-methoxymethyl-3, 5,6-Trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), the compound of the invention 63; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(E) -(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention 64; 2-bromo-4-methoxymethyl-3,5,6 -trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention 65; 2-bromo- 4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans, cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2 ,2-dimethylcyclopropanecarboxylate, compound 66 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-cis-3-[( Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate, the compound of the invention 67; 2-bromo-4-methoxymethyl-3,5 ,6-trifluorobenzyl (1R)-trans, cis-3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (on isomerization of double bonds) Ratio of the product: Z/E = about 2/1), the compound of the invention 68; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl (1R)-trans-3- (2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 2/1), compound 69 of the invention; 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, compound 70 of the invention; 2-bromo-3, 5,6-trifluoro-4-trifluoromethylbenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropane Acid ester, compound 71 of the invention; 4-allyl-2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl) -2,2-dimethylcyclopropanecarboxylate, the compound of the invention 72; 4-allyl-2-bromo-3,5,6-trifluorobenzyl (1R)-trans-3-(1 -propenyl)-2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bonds: Z/E = about 8/1), compound 73 of the invention; 2-bromo-4-propane Alkynyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate, Ben Inventive compound 74; 2-bromo-4-methoxy-3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-di Methylcyclopropanecarboxylate,

＜含Cl酯化合物、含Br酯化合物的製劑化＞ 本發明的有害生物防除劑也能僅本發明化合物(含Cl酯化合物、含Br酯化合物)本身單獨使用，但也能當作如下列的製劑使用。作為該等製劑例如可舉出：蚊香、蚊香片或像蚊香液的加熱蒸散劑、風扇式蚊香、油劑、乳劑、噴霧劑(aerosols)、碳酸氣製劑、可濕性粉劑(wettable powder)、流動劑(flowable agent)(水中懸濁劑、水中乳濁劑等)、微膠囊劑、粉劑、粒劑、錠劑、壓電(piezo)式殺蟲製劑、加熱燻煙劑(自燃型燻煙劑、化學反應型燻煙劑、多孔陶瓷板燻煙劑等)、非加熱蒸散劑(樹脂蒸散劑、紙蒸散劑、不織布蒸散劑、編織物蒸散劑、昇華性錠劑等)、煙霧劑(霧化劑(fogging agent))、直接接觸劑(片狀接觸劑、膠帶狀接觸劑、網狀接觸劑等)、ULV劑及毒餌等。<Formulation of Cl-containing 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 (containing a Cl ester compound or a Br-containing ester compound), but can also be regarded as the following Formulation use. Examples of such preparations include mosquito coils, mosquito-repellent tablets or heated transpiration agents such as mosquito-repellent liquids, fan-type mosquito coils, oils, emulsions, aerosols, carbonic acid preparations, wettable powders, and wettable powders. Flowable agent (suspension in water, opacifier in water, etc.), microcapsules, powders, granules, lozenges, piezo insecticides, heated fumigation agents (self-igniting fumigation) Agent, chemical reaction type smoker, porous ceramic plate smoker, etc.), non-heated transpiration agent (resin transpiration agent, paper transpiration agent, non-woven evapotranspiration, woven fabric transpiration agent, sublimation tablet, etc.), aerosol ( Fogging agent), direct contact agent (sheet contact agent, tape contact agent, mesh contact agent, etc.), ULV agent, poison bait, and the like.

作為製劑化的方法例如可舉出以下的方法。 [1]、依照需要將本發明化合物與固體載體(carrier)、液體載體、氣體狀載體、餌等混合，添加、加工界面活性劑(surfactant)和其他的製劑用輔助劑的方法。 [2]、將本發明化合物含浸於不含有有效成分的基材的方法。 [3]、在混合了本發明化合物及基材後進行成形加工的方法。 在該等製劑也取決於製劑形態，通常以重量比含有0.001~98%的本發明化合物。As a method of formulation, the following methods are mentioned, for example. [1] A method of mixing a compound of the present invention with a solid carrier, a liquid carrier, a gas carrier, a bait or the like as needed, and adding and processing a surfactant and other auxiliary agents for preparation. [2] A method of impregnating a compound of the present invention with a substrate not containing an active ingredient. [3] A method of performing a forming process after mixing the compound of the present invention and a substrate. These preparations also depend on the form of the preparation, and usually contain from 0.001 to 98% by weight of the compound of the invention in a weight ratio.

作為在製劑化時使用的固體載體例如可舉出：黏土類(高嶺黏土(kaolin clay)、矽藻土(diatomaceous earth)、膨土(bentonite)、文挾黏土(Fubasami clay)、酸性白土(acid clay)等)；合成含水氧化矽；滑石(talc)；陶瓷；其他的無機礦物(絹雲母(sericite)、活性碳、碳酸鈣、矽石(silica)等)等的微粉末及粒狀物；常溫下固體的物質(2,4,6-三異丙基-1,3,5-三噁烷(2,4,6-triisopropyl-1,3,5-trioxane)、萘(naphthalene)、對二氯苯(p-dichlorobenzene)、樟腦、金剛烷(adamantine)等)以及由如下的一種或兩種以上構成的氈(felt)：羊毛、絹、棉、麻、紙漿、合成樹脂(例如低密度聚乙烯、線性低密度聚乙烯(linear low density polyethylene)、高密度聚乙烯等的聚乙烯系樹脂；乙烯-乙酸乙烯酯共聚物(ethylene vinyl acetate copolymer)等的乙烯-乙烯酯共聚物(ethylene-vinyl ester copolymer)；乙烯-甲基丙烯酸甲酯共聚物(ethylene-methyl methacrylate copolymer)、乙烯-甲基丙烯酸乙酯共聚物(ethylene-ethyl methacrylate copolymer)等的乙烯-甲基丙烯酸酯共聚物(ethylene methacrylic acid ester copolymer)；乙烯-丙烯酸甲酯共聚物(ethylene-methyl acrylate copolymer)、乙烯-丙烯酸乙酯共聚物(ethylene-ethyl acrylate copolymer)等的乙烯-丙烯酸酯共聚物(ethylene acrylate copolymer)；乙烯-丙烯酸共聚物(ethylene-acrylic acid copolymer)等的乙烯-乙烯基羧酸共聚物(ethylene-vinyl carboxylic acid copolymer)；聚丙烯、丙烯-乙烯共聚物(propylene-ethylene copolymer)等的聚丙烯系樹脂；聚-4-甲基戊烯-1(poly-4-methylpentene-1)、聚丁烯-1(polybutene-1)、聚丁二烯(polybutadiene)、聚苯乙烯(polystyrene)、丙烯腈-苯乙烯樹脂(acrylonitrile‐styrene resin)；丙烯腈-丁二烯-苯乙烯樹脂(acrylonitrile‐butadiene‐styrene resin)、苯乙烯-共軛二烯嵌段共聚物(styrene-conjugated diene block copolymer)、苯乙烯-共軛二烯嵌段共聚物加氫物等的苯乙烯系彈性體(elastomer)；氟樹脂(fluoro resin)；聚甲基丙烯酸甲酯(polymethyl methacrylate)等的丙烯酸系樹脂(acrylic resin)；尼龍6(nylon 6)、尼龍66等的聚醯胺(polyamide)系樹脂；聚對酞酸乙二酯(polyethylene terephthalate)、聚萘二甲酸乙二酯(polyethylene naphthalate)、聚對苯二甲酸丁二酯(polybutylene terephthalate)等的聚酯(polyester)系樹脂；聚碳酸酯(polycarbonate)、聚縮醛(polyacetal)、聚芳酸酯(polyarylate)、羥基苯甲酸聚酯(hydroxybenzoic acid polyester)、聚醚醯亞胺(polyetherimide)、聚酯碳酸酯(polyester carbonate)、聚苯醚(polyphenylene ether)樹脂、聚氯乙烯、聚二氯亞乙烯 (polyvinylidene chloride)、聚氨酯(polyurethane)、發泡聚氨酯、發泡聚丙烯、發泡乙烯等的多孔樹脂)、玻璃、金屬、陶瓷等；纖維；布；針織物；板片(sheet)；紙；紗；發泡體(foam)；多孔體(porous body)及複絲(multifilament)。Examples of the solid carrier used in the formulation include clay (kaolin clay, diatomaceous earth, bentonite, Fubasami clay, acid clay). ))); synthetic aqueous cerium oxide; talc (talc); ceramics; other inorganic minerals (sericite, activated carbon, calcium carbonate, silica, etc.) and other fine powders and granules; The substance of the lower solid (2,4,6-triisopropyl-1,3,5-trioxane, naphthalene, p. P-dichlorobenzene, camphor, adamantine, etc., and felt composed of one or more of the following: wool, crepe, cotton, hemp, pulp, synthetic resin (eg low density poly Ethylene-based resin such as ethylene, linear low-density polyethylene, high-density polyethylene, or ethylene-vinyl acetate copolymer (ethylene-vinyl acetate copolymer) Ester copolymer); ethylene-methyl methacrylate cop Olymer), ethylene methacrylic acid ester copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl acrylate copolymer ) an ethylene-acrylate copolymer such as ethylene-ethyl acrylate copolymer or an ethylene-vinyl carboxylic acid such as ethylene-acrylic acid copolymer (ethylene-vinyl carboxylic acid copolymer); polypropylene-based resin such as polypropylene, propylene-ethylene copolymer; poly-4-methylpentene-1 ), polybutene-1, polybutadiene, polystyrene, acrylonitrile-styrene resin; acrylonitrile-butadiene-styrene Acrylonitrile-butadiene-styrene resin, styrene-conjugated diene block copolymer, styrene-conjugated diene block copolymer A styrene elastomer such as hydrogen; a fluoro resin; an acrylic resin such as polymethyl methacrylate; nylon 6 (nylon 6), nylon 66, etc. Polyamide resin; polyester such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc. (polyester) resin; polycarbonate, polyacetal, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester Polycarbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, foamed polyurethane, expanded polypropylene, foamed vinyl, etc. Resin), glass, metal, ceramic, etc.; fiber; cloth; knitted fabric; sheet; paper; yarn; foam; porous body and multifilament.

作為液體載體例如可舉出：芳香族或脂族烴類(二甲苯、烷基萘(alkylnaphthalene)、苯基二甲苯基乙烷(phenyl xylyl ethane)、煤油(kerosene)、輕油、己烷、環己烷等)；醇類(甲醇、乙醇、異丙醇、丁醇、己醇、苄醇、乙二醇等)；醚類(二***、乙二醇二甲醚(ethylene glycol dimethyl ether)、二乙二醇單***(diethylene glycol monoethyl ether)、二乙二醇單丁醚(diethylene glycol monobutyl ether)、丙二醇單甲醚(propylene glycol monomethyl ether)、四氫呋喃等)；酯類(乙酸乙酯、乙酸丁酯等)；酮類(丙酮、甲基乙基酮、甲基異丁基酮、環己酮等)；腈(nitrile)類(乙腈(acetonitrile)、異丁腈(isobutyronitrile)等)；亞碸(sulfoxide)類(二甲亞碸(dimethyl sulfoxide)等)；醯胺(acid amide)類(N,N-二甲基甲醯胺(N,N-dimethylformamide)、N-甲基-吡咯啶酮(N-methyl-pyrrolidone)等)、碳酸亞烷酯(alkylidene carbonate)類(碳酸丙烯酯(propylene carbonate)等)；植物油(大豆油、棉籽油(cottonseed oil)等)；植物精油(橙油(orange oil)、牛膝草油(hyssop oil)、檸檬油(lemon oil)等)及水。Examples of the liquid carrier include aromatic or aliphatic hydrocarbons (xylene, alkylnaphthalene, phenyl xylyl ethane, kerosene, light oil, hexane, and the like). Cyclohexane, etc.); alcohols (methanol, ethanol, isopropanol, butanol, hexanol, benzyl alcohol, ethylene glycol, etc.); ethers (diethyl ether, ethylene glycol dimethyl ether) , diethylene glycol 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.); nitrile (acetonitrile, isobutyronitrile, etc.); Sulfoxides (dimethyl sulfoxide, etc.); acid amides (N, N-dimethylformamide, N-methyl-pyrrole) N-methyl-pyrrolidone or the like), alkylidene carbonate (propylene carbonate, etc.); Oils (soybean oil, cottonseed oil (cottonseed oil), etc.); vegetable oils (orange oil (orange oil), hyssop oil (hyssop oil), lemon oil (lemon oil), etc.) and water.

作為氣體狀載體例如可舉出：丁烷氣、氟氯碳化物氣體(chlorofluorocarbon)、液化石油氣(LPG(Liquefied Petroleum Gas)、二甲醚及碳酸氣等的壓縮氣體。Examples of the gaseous carrier include a compressed gas of butane gas, chlorofluorocarbon, liquefied petroleum gas (LPG (Liquefied Petroleum Gas), dimethyl ether, and carbonic acid gas).

作為界面活性劑例如可舉出：烷基硫酸酯鹽、烷基磺酸鹽、烷基芳基磺酸鹽、烷基芳基醚類、烷基芳基醚類的聚氧乙烯化物、聚乙二醇醚類、多元醇酯類及糖醇衍生物。Examples of the surfactant include an alkyl sulfate salt, an alkyl sulfonate, an alkyl aryl sulfonate, an alkyl aryl ether, a polyoxyethylene compound of an alkyl aryl ether, and polyethylene. Glycol ethers, polyol esters and sugar alcohol derivatives.

作為其他的製劑用輔助劑可舉出固定劑、分散劑及穩定劑等，具體上例如可舉出：酪蛋白(casein)、明膠(gelatin)、多醣類(澱粉、***膠(gum arabic)、纖維素衍生物、藻酸(alginic acid)等)、木質素(lignin)衍生物、膨土、醣類、合成水溶性聚合物(聚乙烯醇(polyvinyl alcohol)、聚乙烯吡咯啶酮(polyvinylpyrrolidone)、聚丙烯酸等、BHT(2,6-二-三級丁基-4-甲苯酚(2,6-di-tert-butyl-4-methylphenol)及BHA(2-三級丁基-4-甲氧苯酚(2-tert-butyl-4-methoxyphenol)與3-三級丁基-4-甲氧苯酚之混合物)。進而依照需要適宜配合著色劑或香料等也無妨。Examples of the other auxiliary agent for the preparation include a fixing agent, a dispersing agent, a stabilizer, and the like. Specific examples thereof include casein, gelatin, and polysaccharide (starch, gum arabic). , cellulose derivatives, alginic acid, etc., lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone (polyvinylpyrrolidone) ), polyacrylic acid, etc., BHT (2,6-di-tert-butyl-4-methylphenol) and BHA (2-tertiary butyl-4-) A mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol. Further, a coloring agent or a fragrance may be appropriately blended as needed.

作為蚊香的基材例如可舉出：木粉、除蟲菊萃取糟粉等的植物性粉末與紅楠粉、澱粉、羧甲基纖維素(carboxymethyl cellulose)、麩質(gluten)等的結合劑(bonding agent)的混合物。 作為蚊香片的基材例如可舉出：將棉籽絨(cotton linters)凝固成板狀者，及將棉籽絨與紙漿的混合物的原纖維(fibril)凝固成板狀者。 作為自燃型燻煙劑的基材例如可舉出：硝酸鹽、亞硝酸鹽、胍鹽(guanidine salt)、氯酸鉀、硝化纖維素(nitrocellulose)、乙基纖維素、木粉等的燃燒發熱劑；鹼金屬鹽、鹼土金屬鹽的熱分解刺激劑；硝酸鉀等的氧載體(oxygen carrier)；三聚氰胺(melamine)、小麥澱粉等的助燃劑；矽藻土等的增量劑及合成糊料等的結合劑。Examples of the substrate of the mosquito coil include a vegetable powder such as wood powder or pyrethrum extract powder, and a binder of red lotus powder, starch, carboxymethyl cellulose, gluten or the like. a mixture of bonding agents. Examples of the substrate of the mosquito-repellent sheet include those in which cotton linters are solidified into a plate shape, and fibrils in which a mixture of cotton linter and pulp is solidified into a plate shape. Examples of the substrate of the self-igniting fumigation agent include a combustion heat generating agent such as nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose, and wood powder; a thermal decomposition stimulating agent of an alkali metal salt or an alkaline earth metal salt; an oxygen carrier such as potassium nitrate; a combustion aid such as melamine or wheat starch; an extender such as diatomaceous earth; and a synthetic paste. Binding agent.

作為化學反應型燻煙劑的基材例如可舉出：鹼金屬的硫化物、多硫化物、硫氫化物、氧化鈣等的發熱劑；碳化鐵、活化黏土(activated clay)等的觸媒(catalyzer)；偶氮二甲醯胺(azodicarbonamide)、苯磺醯肼(benzenesulfonyl hydrazide)、二硝基五亞甲基四胺(dinitropentamethylenetetramine)、聚苯乙烯、聚氨酯等的有機發泡劑及天然纖維片、合成纖維片等的填充劑。Examples of the substrate of the chemical reaction type smoke generating agent include a heat generating agent such as an alkali metal sulfide, a polysulfide, a sulfurized product, or a calcium oxide; and a catalyst such as iron carbide or activated clay ( Catalyzer); organic foaming agents such as azodicarbonamide, benzenesulfonyl hydrazide, dinitropentamethylenetetramine, polystyrene, polyurethane, etc. A filler such as a synthetic fiber sheet.

作為樹脂蒸散劑等的基材所使用的樹脂例如可舉出：低密度聚乙烯、線性低密度聚乙烯、高密度聚乙烯等的聚乙烯系樹脂；乙烯-乙酸乙烯酯共聚物等的乙烯-乙烯酯共聚物；乙烯-甲基丙烯酸甲酯共聚物、乙烯-甲基丙烯酸乙酯共聚物等的乙烯-甲基丙烯酸酯共聚物；乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物等的乙烯-丙烯酸酯共聚物；乙烯-丙烯酸共聚物等的乙烯-乙烯基羧酸共聚物；聚丙烯、丙烯-乙烯共聚物等的聚丙烯系樹脂；聚-4-甲基戊烯-1、聚丁烯-1、聚丁二烯、聚苯乙烯、丙烯腈-苯乙烯樹脂；丙烯腈-丁二烯-苯乙烯樹脂、苯乙烯-共軛二烯嵌段共聚物、苯乙烯-共軛二烯嵌段共聚物加氫物等的苯乙烯系彈性體；氟樹脂；聚甲基丙烯酸甲酯等的丙烯酸樹脂；尼龍6、尼龍66等的聚醯胺系樹脂；聚對酞酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等的聚酯系樹脂；聚碳酸酯、聚縮醛、聚芳酸酯、羥基苯甲酸聚酯、聚醚醯亞胺、聚酯碳酸酯、聚苯醚樹脂、聚氯乙烯、聚二氯亞乙烯、聚氨酯等，該等基材可單獨使用或以兩種以上的混合物使用，也可以依照需要在該等基材添加鄰苯二甲酸酯(phthalate ester)類(酞酸二甲酯(dimethyl phthalate)、酞酸二辛酯(dioctyl phthalate)等)、己二酸酯(adipic acid ester)類、硬脂酸等的塑化劑。樹脂蒸散劑可藉由將本發明化合物混練於上述基材中後，透過射出成型、擠壓成型、沖壓成型等進行成型而得到。所得到的樹脂製劑依照需要也可更進一步經過成型、剪裁等的程序，加工成板狀、膜狀、膠帶狀、網狀、繩狀等的形狀。該等樹脂製劑例如可當作非加熱蒸散劑、動物用頸圈、動物用耳標、片製劑、引誘膠帶(attractive tape)、引誘繩、園藝用支柱、長期持續性殺蟲網而被加工。Examples of the resin used for the substrate such as a resin transpiration agent include a polyethylene resin such as low density polyethylene, linear low density polyethylene, and high density polyethylene; and ethylene such as ethylene-vinyl acetate copolymer. Vinyl ester copolymer; ethylene-methyl methacrylate copolymer, ethylene-methacrylate copolymer, etc.; ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer Ethylene-acrylate copolymer; ethylene-vinyl carboxylic acid copolymer such as ethylene-acrylic acid copolymer; polypropylene resin such as polypropylene, propylene-ethylene copolymer; poly-4-methylpentene-1 , polybutene-1, polybutadiene, polystyrene, acrylonitrile-styrene resin; acrylonitrile-butadiene-styrene resin, styrene-conjugated diene block copolymer, styrene-total a styrene-based elastomer such as a hydrogenated product of a conjugated diene block copolymer; a fluororesin; an acrylic resin such as polymethyl methacrylate; a polyamine-based resin such as nylon 6, nylon 66; Diester, polyethylene naphthalate, polyterephthalic acid Polyester resin such as diester; polycarbonate, polyacetal, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, poly Vinylethylene oxide, polyurethane, etc., these substrates may be used singly or in combination of two or more kinds, or phthalate esters (dimethyl phthalate) may be added to the substrates as needed. Plasticizers such as (dimethyl phthalate), dioctyl phthalate, etc., adipic acid esters, and stearic acid. The resin transpiration agent can be obtained by kneading the compound of the present invention into the above-mentioned substrate and then molding it by injection molding, extrusion molding, press molding, or 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, or a rope shape by a procedure such as molding or cutting. Such resin preparations can be processed, for example, as non-heated transpiration agents, animal collars, animal ear tags, sheet preparations, attracting tapes, attracting ropes, horticultural pillars, and long-lasting insecticidal nets.

作為毒餌的基材例如可舉出：穀物粉、植物油、醣、結晶纖維素等的餌成分；BHT、降二氫癒創木酸(nordihydroguaiaretic acid)等的抗氧化劑；去氫乙酸(dehydroacetic acid)等的保存劑；辣椒粉末等的防止小孩或寵物誤食之誤食防止劑及起司(cheese)香料、洋蔥香料、花生油等的害蟲引誘性香料。Examples of the substrate of the poison bait include bait components such as cereal flour, vegetable oil, sugar, and crystalline cellulose; antioxidants such as BHT and nordihydroguaiaretic acid; and dehydroacetic acid; A preservative agent such as a pepper powder or the like, a food-preventing agent for preventing eating by a child or a pet, and a pest-inducing fragrance such as cheese flavor, onion flavor, and peanut oil.

本發明化合物也能與其他的殺蟲劑、殺蟎劑、殺菌劑、除草劑、忌避劑(repellent)、協力劑(synergist)、肥料、土壤改良材混用或並用而使用。The compounds of the present invention can also be used in combination with other insecticides, acaricides, bactericides, herbicides, repellents, synergists, fertilizers, soil improving materials or in combination.

作為如此的殺蟲劑、殺蟎劑的有效成分例如可舉出： [1]、擬除蟲菊酯(pyrethroid)系化合物 除蟲菊酯(pyrethrin)、丙烯除蟲菊(allethrin)、普亞列寧(prallethrin)、炔呋菊酯(furamethrin)、列滅寧(resmethrin)、胺菊酯(phthalthrin)、治滅寧(tetramethrin)、依普寧(imiprothrin)、益避寧(empenthrin)、拜富寧(transfluthrin)、美特寧(metofluthrin)、丙氟菊酯(profluthrin)、酚丁滅寧(phenothrin)、賽酚寧(cyphenothrin)、百滅寧(permethrin)、賽滅寧(cypermethrin)、賽扶寧(cyfluthrin)、β-賽扶寧( beta -cyfluthrin)、芬普寧(fenpropathrin)、畢芬寧(bifenthrin)、乙氰菊酯(cycloprothrin)、第滅寧(deltamethrin)、氟氯苯菊酯(flumethrin)、阿納寧(acrinathrin)、泰滅寧(tralomethrin)、賽洛寧(cyhalothrin)、λ-賽洛寧(lambda-cyhalothrin)、汰福寧(tefluthrin)、芬化利(fenvalerate)、福化利(fluvalinate)、依芬寧(etofenprox)、矽護芬(silafluofen)、沒氟菊酯(momfluorothrin)、四氟甲醚菊酯(dimefluthrin)等； [2]、有機磷系化合物 乙醯甲胺磷(acephate)、特嘧硫磷(butathiofos)、大利松(diazinon)、二氯松(dichlorvos：DDVP)、大滅松(dimethoate)、芬殺松(fenthion：MPP)、撲滅松(fenitrothion：MEP)、馬拉松 (malathion)、必芬松(pyridaphenthion)、加護松(propaphos)、三氯松(triclorfon：DEP)等； [3]、胺甲酸酯(carbamate)系化合物 加保利(carbaryl)、加保扶(carbofuran)、丁基滅必蝨(fenobucarb)、滅必蝨(isoprocarb：MIP)、納乃得(methomyl)、NAC、安丹(propoxur：PHC)等； [4]、沙蠶毒素(nereis toxin)系化合物 培丹(cartap)、免速達(bensultap)等； [5]、新菸鹼(neonicotinoid)系化合物 益達胺(imidacloprid)、烯啶蟲胺(nitenpyram)、亞滅培(acetamiprid)、賽速安(thiamethoxam)、賽果培(thiacloprid)、達特南(dinotefuran)、可尼丁(clothianidin)等； [6]、苯甲醯脲(benzoylurea)系化合物 克福隆(chlorfluazuron)、雙三氟蟲脲(bistrifluron)、二福隆(diflubenzuron)、氟芬隆(flufenoxuron)、六伏隆(hexaflumuron)、得福隆(teflubenzuron)、三福隆(triflumuron)等； [7]、苯基吡唑(phenylpyrazole)系化合物 芬普尼(fipronil)、吡啶氟蟲腈(pyriprole)、氟蟲腈(pyrafluprole)等； [8]、肼(hydrazine)系化合物 可芬諾(chromafenozide)、合芬隆(halofenozide)、滅芬諾(methoxyfenozide)等； [9]、天然系殺蟲劑 機油(machine oil)、硫酸化菸鹼(nicotine sulfate)； [10]、其他的殺蟲劑 阿維菌素-B(avermectin-B)、布芬淨(buprofezin)、克凡派(chlorphenapyr)、烯蟲乙酯(hydroprene)、美賜平(methoprene)、因得克(indoxacarb)、惡蟲酮(metoxadiazone)、密滅汀-A (milbemycin-A)、啶蟲丙醚(pyridalyl)、百利普芬(pyriproxyfen)、賜諾殺(spinosad)、氟蟲胺(sulfluramid)、脫芬瑞(tolfenpyrad)、氟大滅(flubendiamide)、賽芬蟎(cyflumetofen)、溴甲烷(methyl bromide)、油酸鉀(potassium oleate)等。Examples of the active ingredient of such an insecticide or acaricide include: [1] pyrethroid-based compound pyrethrin, allethrin, and pueraria. Prallethrin, furamethrin, resmethrin, phthalthrin, tetramethrin, imiprothrin, empenthrin, worshipping (transfluthrin), metofluthrin, profluthrin, phenothrin, cyphenothrin, permethrin, cypermethrin, 赛助Cyfluthrin, beta-cyfluthrin, fenpropathrin, bifenthrin, cycloprothrin, deltamethrin, flumethrin , arrinathrin, tralmethrin, cyhalothrin, lambda-cyhalothrin, tefluthrin, fenvalerate, fuhuali Fluvalinate), etofenprox, silafluofen, moffluorothrin, four Dimefluthrin, etc.; [2], organophosphorus compounds acephate, butathiofos, diazinon, dichlorvos (DDVP), large Dimethoate, fenthion (MPP), fenitrothion (MEP), marathion, pyridaphenthion, propaphos, triclofen (DEP), etc. [3], carbamate compound plus carbaryl, carbofuran, fenobucarb, isoprocarb (MIP), methomyl ), NAC, Anthony (propoxur: PHC), etc.; [4], Nerazes toxin (Cartap), free-speed (bensultap), etc.; [5], neonicotinoid (nenicotinoid) Compound imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloprid, dinotefuran, clothianidin [6], benzoylurea compound chlorfluazuron, bistrifluron, bisflulon ( Diflubenzuron), flufenoxuron, hexaflumuron, teflubenzuron, triflumuron, etc. [7], phenylpyrazole compound fipronil ), pyripramine, pyrafluprole, etc.; [8], hydrazine compounds, chromafenozide, hafenfenzide, methoxyfenozide, etc.; [9], natural insecticide machine oil, nicotine sulfate; [10], other insecticides avermectin-B (avermectin-B), bufenfin (buprofezin ), chlorphenapyr, hydroprene, metheprene, indoxacarb, metoxadiazone, milbemycin-A, pyridine Pyridalyl, pyriproxyfen, spinosad, sulfluramid, tolfenpyrad, flubendiamide, cyflumetofen, Methyl bromide, potassium oleate, and the like.

作為忌避劑的有效成分例如可舉出：N,N-二乙基-間-甲苯醯胺(N,N-diethyl-m-toluamide)、薴(limonene)、沈香醇(linalool)、香茅醛(citronellal)、薄荷腦(menthol)、薄荷酮(menthone)、扁柏醇(hinokitiol)、香葉醇(geraniol)、對薄荷烷-3,8-二醇(p-menthane-3,8-diol)、桉油醇(eucalyptol)、長松針烷-3,4-二醇(carane-3,4-diol)、埃卡瑞丁(icaridin)、IR-3535、MGK-R-326、MGK-R-874等。Examples of the active ingredient of the repellent include N,N-diethyl-m-toluamide, limonene, linalool, and citronellal. (citronellal), menthol, menthone, hinokitiol, geraniol, p-menthane-3, 8-diol , eucalyptol, carane-3,4-diol, icaridin, IR-3535, MGK-R-326, MGK-R- 874 and so on.

作為協力劑的有效成分例如可舉出：5-[2-(2-丁氧基乙氧基)乙氧基甲基]-6-丙基-1,3-苯并二噁唑(5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxole)、N-(2-乙基己基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺(N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-en-2,3-dicarboximide)、八氯二丙醚(octachlorodipropyl ether)、硫氰乙酸異莰酯(isobornyl thiocyanoacetate)、N-(2-乙基己基)-1-異丙基-4-甲基雙環[2.2.2]辛-5-烯-2,3-二羧基醯亞胺(N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo[2.2.2]oct-5-en-2,3-dicarboximide)等。The active ingredient of the synergist is, for example, 5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzobisoxazole (5- [2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxole), N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene 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-dicarboxyarmine (N-(2-ethylhexyl)- 1-isopropyl-4-methylbicyclo [2.2.2] oct-5-en-2, 3-dicarboximide) and the like.

作為本發明化合物具有效力的有害生物例如可舉出有害昆蟲或有害蟎等的有害節肢動物，具體上可舉出以下者。 雙翅目害蟲：淡色庫蚊、三斑家蚊、地下家蚊、熱帶家蚊等的家蚊類；埃及斑蚊、白線斑蚊等的斑蚊類；雷氏按蚊、中華按蚊等的瘧蚊類；搖蚊類；家蠅、畜廄腐蠅、黃腹廁蠅等的家蠅類；綠頭蠅類；肉蠅類；種蠅、蔥蠅等的花蠅類；果蠅類；潛蠅類；醋蠅類；蝶蠅類；蚤蠅類；虻類；黑蚊類；螫蠅類；蠓類等； 網翅目害蟲：德國蟑螂、煙色蟑螂、美洲蟑螂、褐色蟑螂、東方蟑螂等； 膜翅目害蟲：蟻類、大黃蜂類、蟻形蜂類、菜葉蜂等的葉蜂類； 隱翅目害蟲：狗蚤、貓蚤、人蚤等； 蝨亞目害蟲：人蝨、陰蝨、頭蝨、體蝨等； 等翅目害蟲：散白蟻、家白蟻等； 半翅目害蟲：斑飛蝨、稻褐飛蝨等的飛蝨類；黑尾葉蟬等的葉蟬類；棉蚜等的蚜蟲類；椿象類；臭蟲等的臭蟲類等； 鱗翅目害蟲：二化螟蛾、瘤野螟蛾等的螟蛾類；斜紋夜蛾、夜盜蛾、甘藍夜蛾等的夜盜蛾類；蘋果蠹蛾、潛葉蛾、黃毒蛾類；小菜蛾、稻弄蝶、衣蛾、袋衣蛾等； 鞘翅目害蟲：姬鰹節蟲、姬圓鰹節蟲、米象鼻蟲、小豆象鼻蟲等的象鼻蟲類；大黃粉蟲、擬榖盜等的擬步行蟲類；番死蟲類；粉蠹蟲類等； 蟎類：美洲室塵蟎、歐洲室塵螨等的室塵蟎類；腐食酪蟎、橢圓斑白蟎等的粉蟎類；食甜蟎、家食甜蟎、粉塵蟎等的食甜蟎類；馬六甲肉食蟎(cheyletus malaccensis)、馬六甲肉食蟎(cheyletus malaccensis oudemans)等的肉食蟎類；細蟎類；嗜草蟎類；簡單縫甲蟎類；長角血蜱等的硬蜱類；北部禽蟎、雞皮刺蟎等的雞皮刺蟎類。Examples of the harmful organism having efficacy as the compound of the present invention include harmful insects or harmful arthropods such as harmful mites, and specific examples thereof include the following. Diptera pests: domestic mosquitoes such as Culex pipiens, Trichosanthes, underground mosquitoes, tropical mosquitoes, etc.; mosquitoes such as Egyptian and white-spotted mosquitoes; Anopheles sinensis, Anopheles sinensis, etc. Malaria mosquitoes; housefly, domestic flies, housefly, fly, yellow-bellied flies, etc.; green-headed flies; flies; flies, flies, onions, etc.; fruit flies; Lepidoptera; vinegar flies; butterfly flies; ticks; mites; black mosquitoes; scorpion flies; mites, etc; nettle pests: German cockroach, smoky cockroach, American cockroach, brown cockroach, oriental蟑螂 ;; Hymenoptera pests: ants, hornets, ant bees, leaf bees, etc.; genus Pseudoptera: scorpion, meerkat, ape, etc.;虱, 虱, head 虱, body 虱, etc.; Isoptera pests: white termites, house termites, etc.; Hemiptera pests: locusts, rice brown planthoppers, etc.; Aphids such as cotton aphid; mites; nymphs such as bed bugs; lepidopteran pests: cockroach moths such as the cockroach moth, the cockroach moth, etc.; Nocturnal moths such as the night moth; apple moth, leaf miner, yellow moth; Plutella xylostella, rice butterfly, cloth moth, Coat moth, etc.; Coleoptera pest: 鲣 鲣 、, 鲣 鲣 、, rice Weevils such as weevil and small bean weevil; pseudo-walking insects such as rhododendron and locusts; dead insects; white mites; mites: American dust mites, European chamber Dust mites such as dust mites; white mites such as rotted casein and elliptic leukoplakia; sweet mites such as sweet glutinous rice, sweet-smelling glutinous rice, and dust mites; malay scorpion (cheyletus malaccensis), malacca meat Carp mites such as che (cheyletus malaccensis oudemans); scorpion scorpion; scorpion scorpion; simple scorpion scorpion; hard scorpion .

本發明的有害生物的防除方法是藉由在通常本發明的有害生物防除劑的形態中，將本發明化合物的有效量施用於有害生物或有害生物的棲息地而進行。 作為本發明的有害生物防除劑的施用方法例如可舉出以下的方法，可依照本發明的有害生物防除劑的形態、使用場所等適宜選擇。 [1]、在有害生物或有害生物的棲息地原封不動地對本發明的有害生物防除劑進行處理之方法。 [2]、在以水等的溶劑將本發明的有害生物防除劑稀釋後，在有害生物或有害生物的棲息地對本發明的有害生物防除劑進行散布處理之方法。 在此情形下，通常將被製劑化成乳劑、可濕性粉劑、流動劑、微膠囊劑製劑等的本發明的有害生物防除劑稀釋以使本發明化合物的濃度成為0.1~10000ppm。 [3]、在有害生物的棲息地藉由加熱等的手段(means)使本發明的有害生物防除劑的有效成分揮散之方法。 此情形，本發明化合物的施用量、施用濃度都可依照本發明的有害生物防除劑的形態、施用時期、施用場所、施用方法、有害生物的種類、被害狀況等適宜決定。The method for controlling a pest of the present invention is carried out by applying an effective amount of the compound of the present invention to a habitat of a pest or a pest in the form of the pest control agent of the present invention. The method of applying the pest control agent of the present invention is, for example, the following method, and can be appropriately selected according to the form of the pest control agent of the present invention, the place of use, and the like. [1] A method of treating a pest control agent of the present invention intact in a habitat of a pest or a pest. [2] A method of dispersing the pest control agent of the present invention in a habitat of a pest or a 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, a wettable powder, a flowable agent, a microcapsule preparation or the like is usually diluted so that the concentration of the compound of the present invention becomes 0.1 to 10000 ppm. [3] A method of volatilizing an active ingredient of the pest control agent of the present invention by means of heating or the like in a habitat of a pest. In this case, the application amount and application concentration of the compound of the present invention can be appropriately determined according to the form of the pest control agent of the present invention, the application period, the application site, the application method, the type of the pest, the damage state, and the like.

以本發明化合物當作害蟲防除用使用的情形其施用量適用於空間時為作為本發明化合物的量通常為0.001~100mg/m3 ，適用於平面時為0.001~100mg/m2 。蚊香、蚊香片等是依照其製劑形態藉由加熱使有效成分揮散而施用。樹脂蒸散劑、紙蒸散劑、不織布蒸散劑、編織物蒸散劑、昇華性錠劑等可藉由原封不動地放置於例如施用的空間，以及在送風下設置於該製劑而使用。 作為以本發明的有害生物防除組成物當作害蟲防除用而施用的空間，例如可舉出：起居室、餐廳、臥室、儲藏室(closet)、壁櫥、日式衣櫃、櫥櫃、廁所、澡堂、庫房、倉庫、車內等，進而也能在野外的開放空間施用。When the compound of the present invention as used in the case of insect pest control by an amount which is suitable for administration as a space for the amount of the compound of the present invention is generally 0.001 ~ 100mg / m 3, is applied to the plane 0.001 ~ 100mg / m 2. Mosquito coils, mosquito-repellent tablets, and the like are applied by volatilizing the active ingredient by heating according to the form of the preparation. A resin transpiration agent, a paper transpiration agent, a non-woven transpiration agent, a woven fabric transpiration agent, a sublimation tablet, or the like can be used by being placed in a space such as application as it is, and being placed in the preparation under air supply. The space to which the pest control composition of the present invention is applied as pest control can be, for example, a living room, a dining room, a bedroom, a closet, a closet, a Japanese wardrobe, a cabinet, a toilet, a bathhouse, Treasury, warehouses, cars, etc., can also be applied in open spaces in the wild.

將本發明的有害生物防除組成物使用於牛、馬、豬、羊、山羊、雞等的家畜，狗、貓、大鼠、小鼠等的小動物的外部寄生蟲防除的情形，能以獸醫學上眾所周知的方法使用於動物。作為具體的使用方法，在以全身抑制(systemic control)作為目的的情形下，例如藉由錠劑、飼料混入、栓劑、注射(筋肉內、皮下、靜脈內、腹腔內等)進行給藥，在以非全身的抑制(non-systemic control)作為目的的情形下，例如藉由噴霧油劑或水性液劑之澆注(pour-on)處理或點注(spot-on)處理之以洗毛製劑清洗動物或將樹脂蒸散劑作成頸圈或耳標裝在動物等之方法使用。給藥在動物體的情形之本發明化合物的量通常相對於動物之體重1kg為0.01~100mg的範圍。 [實施例]The pest control composition of the present invention is used in livestock of cattle, horses, pigs, sheep, goats, chickens, and the like, and the external parasites of small animals such as dogs, cats, rats, and mice are controlled by veterinary medicine. The well known method is used in animals. As a specific method of use, in the case of systemic control, for example, by administration of a tablet, a feed, a suppository, an injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), In the case of non-systemic control, for example, a pour-on treatment or a spot-on treatment by a spray oil or an aqueous liquid is used to wash the scouring preparation. The animal may be used as a method in which a resin transpiration agent is used as a collar or an ear tag in an animal or the like. The amount of the compound of the present invention administered in the case of an animal is usually in the range of 0.01 to 100 mg with respect to 1 kg of the body weight of the animal. [Examples]

以下藉由製造例、製劑例及效果試驗例等更詳細地說明本發明，但本發明不是被限定於該等的例子。Hereinafter, the present invention will be described in more detail by way of Production Examples, Preparation Examples, Effect Test Examples, and the like, but the present invention is not limited to the examples.

＜含Cl酯化合物的實施例＞ 顯示本發明化合物(含Cl酯化合物)的製造例。<Example of Cl-containing ester compound> A production example of the compound of the present invention (containing a Cl ester compound) is shown.

製造例1：化合物(9)的製造 在冰冷下將二異丁基氫化鋁(1.5M 甲苯溶液、2.4mL、3.60mmol)滴下到甲基 2-氯-3,5,6-三氟苯甲酸酯(316mg、1.41mmol)的甲苯(5mL)及四氫呋喃(5mL)的混合溶液。在冰冷下攪拌2小時後，將反應液注加到1N鹽酸水溶液及水，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析(silica gel column chromatography)，得到以下列的式[化19](9)表示的2-氯-3,5,6-三氟苯甲醇266mg：Production Example 1: Production of Compound (9) Diisobutylaluminum hydride (1.5 M solution in toluene, 2.4 mL, 3.60 mmol) was added dropwise to methyl 2-chloro-3,5,6-trifluorobenzene under ice cooling. A mixed solution of an acid ester (316 mg, 1.41 mmol) in toluene (5 mL) and tetrahydrofuran (5 mL). After stirring for 2 hours under ice cooling, the reaction mixture was poured into 1N aqueous hydrochloric acid and water, and extracted with ethyl acetate. After the organic layer was dried over magnesium sulfate, the residue was concentrated under reduced pressure, and the residue was applied to silica gel column chromatography to give 2-chlorobenzene represented by the following formula [19] (9). -3,5,6-trifluorobenzyl alcohol 266 mg:

[化19]。[Chemistry 19] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.04(t，1H)、4.88(dd，2H)、7.03(m，1H)White solid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 2.04 (t, 1H), 4.88 (dd, 2H), 7.03 (m, 1H)

製造例2：化合物(10)的製造 在室溫下將三乙胺(1.9mL、13.65mmol)、苯甲胺(1.00g、9.33mmol)依次滴下到甲基 4-甲基-2,3,5,6-四氟苯甲酸酯(1.01g、4.55mmol)的甲苯(15mL)溶液。在100℃下攪拌10小時後，將水注加到反應液，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化20](10)表示的甲基 2-苄胺基-4-甲基-3,5,6-三氟苯甲酸酯1.18g：Production Example 2: Production of Compound (10) Triethylamine (1.9 mL, 13.65 mmol) and benzylamine (1.00 g, 9.33 mmol) were successively dropped to methyl 4-methyl-2,3 at room temperature. A solution of 5,6-tetrafluorobenzoate (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give methyl 2-benzylamino-4 as the formula (20) (10) below. -Methyl-3,5,6-trifluorobenzoate 1.18g:

[化20]。[Chemistry 20] .

黃色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.21(m，3H)、3.88(s，3H)、4.50(m，2H)、6.96(brs，1H)、7.29(m，5H)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)

製造例3：化合物(11)的製造 在室溫下將鈀碳(117mg)注加到甲基 2-苄胺基-4-甲基-3,5,6-三氟苯甲酸酯(1.15g、3.72mmol)的乙酸乙酯(50mL)溶液，在氫環境下取代反應液。在氫環境下在室溫下攪拌3小時後，對反應液進行矽藻土過濾後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化21](11)表示的甲基 2-胺基-4-甲基-3,5,6-三氟苯甲酸酯690mg：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) at room temperature. A solution of g, 3.72 mmol) in ethyl acetate (50 mL) was evaporated in vacuo. After stirring at room temperature for 3 hours in a hydrogen atmosphere, the reaction liquid was filtered through celite, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain the following formula (21). 11) Methyl 2-amino-4-methyl-3,5,6-trifluorobenzoate 690 mg:

[化21]。[Chem. 21] .

黃色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.24(m，3H)、3.92(s，3H)、5.55(brs，2H)Yellow liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 2.24 (m, 3H), 3.92 (s, 3H), 5.55 (brs, 2H)

製造例4：化合物(12)的製造 在冰冷下將亞硝酸鈉(213mg、3.10mmol)的水(7mL)溶液慢慢地添加到甲基 2-胺基-4-甲基-3,5,6-三氟苯甲酸酯(678mg、3.10mmol)的醋酸(7mL)與濃鹽酸(14mL)的混合溶液。在反應液同溫度下攪拌50分。在冰冷下遍及2分將氯化銅(I)(612mg、3.10mmol)分割添加於反應液。在室溫下攪拌12小時後，將水注加到反應液，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化22](12)表示的甲基 2-氯-4-甲基-3,5,6-三氟苯甲酸酯505mg：Production Example 4: Preparation of Compound (12) 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 under ice cooling. A mixed solution of 6-trifluorobenzoate (678 mg, 3.10 mmol) in acetic acid (7 mL) and concentrated hydrochloric acid (14 mL). The reaction solution was stirred at the same temperature for 50 minutes. Copper (I) chloride (612 mg, 3.10 mmol) was added to the reaction liquid in portions over 2 minutes under ice cooling. After stirring at room temperature for 12 hours, water was added to the reaction liquid, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain methyl 2-chloro-4-methyl represented by the following formula [22] (12). Base-3,5,6-trifluorobenzoate 505mg:

[化22]。[化22] .

黃色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.29(m，3H)、3.98(s，3H)Yellow liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 2.29 (m, 3H), 3.98 (s, 3H)

製造例5：化合物(13)的製造 在冰冷下將二異丁基氫化鋁(1.5M 甲苯溶液、3.5mL、5.25mmol)滴下到甲基 2-氯-4-甲基-3,5,6-三氟苯甲酸酯(502mg、2.10mmol)的甲苯(5mL)及四氫呋喃(5mL)的混合溶液。在冰冷下攪拌1小時後，將反應液注加到1N鹽酸水溶液及水，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化23](13)表示的2-氯-4-甲基-3,5,6-三氟苯甲醇410mg：Production Example 5: Production of Compound (13) Diisobutylaluminum hydride (1.5 M toluene solution, 3.5 mL, 5.25 mmol) was added dropwise to methyl 2-chloro-4-methyl-3,5,6 under ice cooling. A mixed solution of trifluorobenzoic acid ester (502 mg, 2.10 mmol) in toluene (5 mL) and tetrahydrofuran (5 mL). After stirring for 1 hour under ice cooling, the reaction mixture was poured into 1N aqueous hydrochloric acid and water, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methyl- represented by the following formula [23] (13). 3,5,6-trifluorobenzyl alcohol 410 mg:

[化23]。[化23] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.99(t，1H)、2.27(m，3H)、4.85(dd，2H)White solid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.99 (t, 1H), 2.27 (m, 3H), 4.85 (dd, 2H)

製造例6：化合物(14)的製造 在室溫下將三乙胺(3.4mL、24.53mmol)、苯甲胺(1.73g、16.14mmol)依次滴下到甲基 4-甲氧基甲基-2,3,5,6-四氟苯甲酸酯(2.03g、8.06mmol)的甲苯(20mL)溶液。在100℃下攪拌7小時後，將水注加到反應液，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化24](14)表示的甲基 2-苄胺基-4-甲氧基甲基-3,5,6-三氟苯甲酸酯2.32g：Production Example 6: Production of Compound (14) Triethylamine (3.4 mL, 24.53 mmol) and benzylamine (1.73 g, 16.14 mmol) were successively dropped to methyl 4-methoxymethyl-2 at room temperature. , a solution of 3,5,6-tetrafluorobenzoate (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give methyl 2-benzylamino-4 as the formula (24). -Methoxymethyl-3,5,6-trifluorobenzoate 2.32g:

[化24]。[Chem. 24] .

黃色液體：1 H-NMR(CDCl3 ，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)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)

製造例7：化合物(15)的製造 在室溫下將鈀碳(230mg)注加到甲基 2-苄胺基-4-甲氧基甲基-3,5,6-三氟苯甲酸酯(2.32g、6.84mmol)的乙酸乙酯(80mL)溶液，在氫環境下取代反應液。在氫環境下在室溫下攪拌3小時後，對反應液進行矽藻土過濾後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化25](15)表示的甲基 2-胺基-4-甲氧基甲基-3,5,6-三氟苯甲酸酯1.12g：Production Example 7: Production of Compound (15) Palladium carbon (230 mg) was added to methyl 2-benzylamino-4-methoxymethyl-3,5,6-trifluorobenzoic acid at room temperature. A solution of the ester (2.32 g, 6.84 mmol) in ethyl acetate (80 mL) was evaporated in vacuo. After stirring at room temperature for 3 hours in a hydrogen atmosphere, the reaction solution was filtered through Celite, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give the following formula (25). 15) Methyl 2-amino-4-methoxymethyl-3,5,6-trifluorobenzoate 1.12 g:

[化25]。[化25] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：3.40(s，3H)、3.94(s，3H)、4.56(m，2H)、5.59(brs，2H)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)

製造例8：化合物(16)的製造 在冰冷下將亞硝酸鈉(91mg、1.32mmol)的水(4mL)溶液慢慢地添加到甲基 2-胺基-4-甲氧基甲基-3,5,6-三氟苯甲酸酯(326mg、1.31mmol)的醋酸(4mL)與濃鹽酸(8mL)的混合溶液。在反應液同溫度下攪拌50分。在冰冷下遍及2分將氯化銅(I)(259mg、2.62mmol)分割添加於反應液。在室溫下攪拌5小時後，將水注加到反應液，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化26](16)表示的甲基 2-氯-4-甲氧基甲基-3,5,6-三氟苯甲酸酯135mg：Production Example 8: Preparation of Compound (16) A solution of sodium nitrite (91 mg, 1.32 mmol) in water (4 mL) was slowly added to methyl 2-amino-4-methoxymethyl-3 under ice cooling. A mixed solution of 5,6-trifluorobenzoate (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. Copper (I) chloride (259 mg, 2.62 mmol) was added to the reaction liquid over 2 minutes under ice cooling. After stirring at room temperature for 5 hours, water was added to the reaction liquid, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain methyl 2-chloro-4-methyl represented by the following formula [26] (16). Oxymethyl-3,5,6-trifluorobenzoate 135 mg:

[化26]。[Chem. 26] .

黃色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：3.39(s，3H)、4.00(s，3H)、4.58(m，2H)Yellow liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 3.39 (s, 3H), 4.00 (s, 3H), 4.58 (m, 2H)

製造例9：化合物(17)的製造 在冰冷下將二異丁基氫化鋁(1.5M 甲苯溶液、1.0mL、1.50mmol)滴下到甲基 2-氯-4-甲氧基甲基-3,5,6-三氟苯甲酸酯(130mg、0.48mmol)的甲苯(3mL)及四氫呋喃(3mL)的混合溶液。在冰冷下攪拌1小時後，將反應液注加到1N鹽酸水溶液及水，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化27](17)表示的2-氯-4-甲氧基甲基-3,5,6-三氟苯甲醇67mg：Production Example 9 Production of Compound (17) Diisobutylaluminum hydride (1.5 M toluene solution, 1.0 mL, 1.50 mmol) was added dropwise to methyl 2-chloro-4-methoxymethyl-3 under ice cooling. A mixed solution of 5,6-trifluorobenzoate (130 mg, 0.48 mmol) in toluene (3 mL) and tetrahydrofuran (3 mL). After stirring for 1 hour under ice cooling, the reaction mixture was poured into 1N aqueous hydrochloric acid and water, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and concentrated under reduced pressure. The residue was applied to a silica gel column chromatography to give 2-chloro-4-methoxy group represented by the following formula [27] (17). Methyl-3,5,6-trifluorobenzyl alcohol 67mg:

[化27]。[化27] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.03(t，1H)、3.39(s，3H)、4.58(m，2H)、4.88(dd，2H)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)

製造例10：本發明化合物C1的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(54mg、0.28mmol)及4-二甲胺基吡啶(3mg)加到2-氯-3,5,6-三氟苯甲醇(50mg、0.26mmol)及(1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷甲酸(47mg、0.28mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌24小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化28](18)表示的2-氯-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物C1)21mg：Production Example 10: Production of Compound C1 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (54 mg, 0.28 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-chloro-3,5,6-trifluorobenzyl alcohol (50 mg, 0.26 mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2- A solution of dimethylcyclopropanecarboxylic acid (47 mg, 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-3,5,6 represented by the following formula [28] (18). -trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compound C1 of the invention) 21 mg:

[化28]。[化28] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例11：本發明化合物I1的製造 將吡啶(100mg、1.20mmol)、(1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙甲醯氯(76mg、0.34mmol)及4-二甲胺基吡啶(3mg)依次加到2-氯-3,5,6-三氟苯甲醇(40mg、0.20mmol)的四氫呋喃溶液(2mL)。在室溫下攪拌19小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化29](19)表示的2-氯-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物I1)75mg：Production Example 11: Production of Compound I1 of the Present Invention Pyridine (100 mg, 1.20 mmol), (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethyl ring Propylguanidine chloride (76 mg, 0.34 mmol) and 4-dimethylaminopyridine (3 mg) were added to a solution of 2-chloro-3,5,6-trifluorobenzyl alcohol (40 mg, 0.20 mmol) in tetrahydrofuran (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-3,5,6 represented by the following formula [29] (19). -trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate (Compound I1 of the invention) 75 mg:

[化29]。[化29] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例12：本發明化合物P1的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(53mg、0.28mmol)及4-二甲胺基吡啶(3mg)加到2-氯-3,5,6-三氟苯甲醇(45mg、0.23mmol)及(1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷甲酸(關於雙鍵的異構物的比率：Z/E=約8/1)(53mg、0.34mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌20小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化30](20)表示的2-氯-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物P1)(關於雙鍵的異構物的比率：Z/E=約8/1)29mg：Production Example 12: Production of Compound P1 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (53 mg, 0.28 mmol) and 4-dimethylaminopyridine ( 3 mg) to 2-chloro-3,5,6-trifluorobenzyl alcohol (45 mg, 0.23 mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane A solution of formic acid (ratio of the isomer of the double bond: Z/E = about 8/1) (53 mg, 0.34 mmol) in chloroform (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain 2-chloro-3,5,6 represented by the following formula [30] (20). -Trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Compound P1 of the invention) (ratio of isomers with respect to double bonds: Z/E = about 8/1) 29mg:

[化30]。[化30] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.14(s，3H，Z+E體)、1.28(s，3H，Z+E體)、1.46(d，1H，Z+E體)、1.70(dd，3H，Z+E體)、2.18(m，1H，Z+E體)、5.11(m，1H，Z+E體)、5.29(m，2H，Z+E體)、5.60(m，1H，Z+E體)、7.08(m，1H，Z+E體)Colorless liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.14 (s, 3H, Z+E), 1.28 (s, 3H, Z+E), 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)

製造例13：本發明化合物R1的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(37mg、0.19mmol)及4-二甲胺基吡啶(3mg)加到2-氯-3,5,6-三氟苯甲醇(31mg、0.16mmol)及(1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷甲酸(40mg、0.19mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌24小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化31](21)表示的2-氯-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯(本發明化合物R1)33mg：Production Example 13: Production of Compound R1 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (37 mg, 0.19 mmol) and 4-dimethylaminopyridine ( 3 mg) to 2-chloro-3,5,6-trifluorobenzyl alcohol (31 mg, 0.16 mmol) and (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl) a solution of 2,2-dimethylcyclopropanecarboxylic 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. The organic layer was dried over magnesium sulfate, and concentrated under reduced pressure. The residue was applied to a silica gel column chromatography to give 2-chloro-3,5,6 represented by the following formula [31] (21). -trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate (compound R1 of the invention) ) 33mg:

[化31]。[化31] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例14：本發明化合物T1的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(37mg、0.19mmol)及4-二甲胺基吡啶(3mg)加到2-氯-3,5,6-三氟苯甲醇(30mg、0.15mmol)及(1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷甲酸(40mg、0.20mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌24小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化32](22)表示的2-氯-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯(本發明化合物T1)47mg：Production Example 14: Production of Compound T1 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (37 mg, 0.19 mmol) and 4-dimethylaminopyridine ( 3 mg) added to 2-chloro-3,5,6-trifluorobenzyl alcohol (30 mg, 0.15 mmol) and (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl a solution of 2,2-dimethylcyclopropanecarboxylic acid (40 mg, 0.20 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain 2-chloro-3,5,6 represented by the following formula [32] (22). -trifluorobenzyl (1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate (Compound T1 of the invention) ) 47mg:

[化32]。[化32] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例15：本發明化合物W1的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(83mg、0.43mmol)及4-二甲胺基吡啶(3mg)加到2-氯-3,5,6-三氟苯甲醇(70mg、0.36mmol)及2,2,3,3-四甲基環丙烷甲酸(61mg、0.43mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌24小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化33](23)表示的2-氯-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯(本發明化合物W1)72mg：Production Example 15: Production of Compound W1 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (83 mg, 0.43 mmol) and 4-dimethylaminopyridine ( 3 mg) to a solution of 2-chloro-3,5,6-trifluorobenzyl alcohol (70 mg, 0.36 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (61 mg, 0.43 mmol) in chloroform (3mL). After stirring at room temperature for 24 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-3,5,6 represented by the following formula [33] (23). -trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (Compound W1 of the invention) 72 mg:

[化33]。[化33] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.17(s，7H)、1.25(s，6H)、5.24(m，2H)、7.08(m，1H)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)

製造例16：本發明化合物C2的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(59mg、0.31mmol)及4-二甲胺基吡啶(3mg)加到2-氯-4-甲基-3,5,6-三氟苯甲醇(50mg、0.24mmol)及(1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷甲酸(52mg、0.31mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌6小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化34](24)表示的2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物C2)53mg：Production Example 16: Production of Compound C2 of the Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (59 mg, 0.31 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-chloro-4-methyl-3,5,6-trifluorobenzyl alcohol (50 mg, 0.24 mmol) and (1R)-trans-3-(2-methyl-1-propenyl) -2,2-Dimethylcyclopropanecarboxylic acid (52 mg, 0.31 mmol) in chloroform (3 mL). After stirring at room temperature for 6 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methyl- represented by the following formula [34] (24). 3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compound C2 of the present invention) 53 mg :

[化34]。[化34] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例17：本發明化合物I2的製造 將吡啶(112mg、1.42mmol)、(1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙甲醯氯(191mg、0.36mmol)及4-二甲胺基吡啶(3mg)依次加到2-氯-4-甲基-3,5,6-三氟苯甲醇(50mg、0.24mmol)的四氫呋喃溶液(2mL)。在室溫下攪拌7小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化35](25)表示的2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物I2)60mg：Production Example 17: Production of Compound I2 of the Present Invention Pyridine (112 mg, 1.42 mmol), (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethyl ring Propargyl chloride (191 mg, 0.36 mmol) and 4-dimethylaminopyridine (3 mg) were added sequentially to 2-chloro-4-methyl-3,5,6-trifluorobenzyl alcohol (50 mg, 0.24 mmol). Tetrahydrofuran solution (2 mL). After stirring at room temperature for 7 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methyl- represented by the following formula [35] (25). 3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate (Compound I2 of the invention) ) 60mg:

[化35]。[化35] .

白色固體：1 H-NMR(CDCl3 ，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)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)

製造例18：本發明化合物P2的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(49mg、0.26mmol)及4-二甲胺基吡啶(2mg)加到2-氯-4-甲基-3,5,6-三氟苯甲醇(41mg、0.19mmol)及(1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷甲酸(關於雙鍵的異構物的比率：Z/E=約8/1)(39mg、0.25mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌19小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化36](26)表示的2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物P2)(關於雙鍵的異構物的比率：Z/E=約8/1)24mg：Production Example 18: Production of Compound P2 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (49 mg, 0.26 mmol) and 4-dimethylaminopyridine ( 2 mg) was added to 2-chloro-4-methyl-3,5,6-trifluorobenzyl alcohol (41 mg, 0.19 mmol) and (1R)-trans-3-(1-propenyl)-2,2- A solution of dimethylcyclopropanecarboxylic acid (ratio of the isomer of the double bond: Z/E = about 8/1) (39 mg, 0.25 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. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure. The residue was applied to a silica gel column chromatography to give 2-chloro-4-methyl- represented by the following formula [36] (26). 3,5,6-trifluorobenzyl(1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compound P2 of the invention) (depending on the double bond) Structure ratio: Z/E = about 8/1) 24 mg:

[化36]。[化36] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.13(s，3H，Z+E體)、1.28(s，3H，Z+E體)、1.45(d，1H，Z+E體)、1.70(dd，3H，Z+E體)、2.17(m，1H，Z+E體)、2.28(m，3H，Z+E體)、5.11(m，1H，Z+E體)、5.27(m，2H，Z+E體)、5.59(m，1H，Z+E體)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)

製造例19：本發明化合物R2的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(41mg、0.21mmol)及4-二甲胺基吡啶(3mg)加到2-氯-4-甲基-3,5,6-三氟苯甲醇(35mg、0.17mmol)及(1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷甲酸(46mg、0.22mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌21小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化37](27)表示的2-氯-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-[(E)-(2-甲氧羰基-1-丙烯基)]-2,2-二甲基環丙烷羧酸酯(本發明化合物R2)58mg：Production Example 19: Production of Compound R2 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (41 mg, 0.21 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-chloro-4-methyl-3,5,6-trifluorobenzyl alcohol (35 mg, 0.17 mmol) and (1R)-trans-3-[(E)-(2-methoxycarbonyl) A solution of 1,3-propenyl)]-2,2-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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methyl- represented by the following formula [37] (27). 3,5,6-trifluorobenzyl (1R)-trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate (Compound R2 of the invention) 58 mg:

[化37]。[化37] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例20：本發明化合物T2的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(36mg、0.19mmol)及4-二甲胺基吡啶(3mg)加到2-氯-4-甲基-3,5,6-三氟苯甲醇(30mg、0.14mmol)及(1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷甲酸(37mg、0.19mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌14小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化38](28)表示的2-氯-4-甲基-3,5,6-三氟苄基 (1R)-順式-3-[(Z)-(2-甲氧羰基-1-乙烯基)]-2,2-二甲基環丙烷羧酸酯(本發明化合物T2)38mg：Production Example 20: Production of Compound T2 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (36 mg, 0.19 mmol) and 4-dimethylaminopyridine ( 3 mg) to 2-chloro-4-methyl-3,5,6-trifluorobenzyl alcohol (30 mg, 0.14 mmol) and (1R)-cis-3-[(Z)-(2-methoxycarbonyl) 1-(Vinyl)]-2,2-dimethylcyclopropanecarboxylic acid (37 mg, 0.19 mmol) in chloroform (2 mL). After stirring at room temperature for 14 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methyl- represented by the following formula [38] (28). 3,5,6-trifluorobenzyl(1R)-cis-3-[(Z)-(2-methoxycarbonyl-1-vinyl)]-2,2-dimethylcyclopropanecarboxylate (Compound T2 of the invention) 38 mg:

[化38]。[化38] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例21：本發明化合物W2的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(41mg、0.21mmol)及4-二甲胺基吡啶(3mg)加到2-氯-4-甲基-3,5,6-三氟苯甲醇(35mg、0.17mmol)及2,2,3,3-四甲基環丙烷甲酸(31mg、0.22mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌19小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化39](29)表示的2-氯-4-甲基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯(本發明化合物W2)49mg：Production Example 21: Production of Compound W2 of the Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (41 mg, 0.21 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-chloro-4-methyl-3,5,6-trifluorobenzyl alcohol (35 mg, 0.17 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (31 mg, 0.22 mmol) A solution of 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methyl- represented by the following formula [39] (29). 3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (Compound W2 of the invention) 49 mg:

[化39]。[39] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.17(s，7H)、1.25(s，6H)、2.28(m，3H)、5.22(m，2H)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)

製造例22：本發明化合物C3的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(20mg、0.10mmol)及4-二甲胺基吡啶(2mg)加到2-氯-4-甲氧基甲基-3,5,6-三氟苯甲醇(16mg、0.07mmol)及(1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷甲酸(17mg、0.10mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌15小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化40](30)表示的2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物C3)14mg：Production Example 22: Production of Compound C3 of the Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (20 mg, 0.10 mmol) and 4-dimethylaminopyridine ( 2 mg) was added to 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (16 mg, 0.07 mmol) and (1R)-trans-3-(2-methyl-1- A solution of propylene)-2,2-dimethylcyclopropanecarboxylic 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain 2-chloro-4-methoxy group represented by the following formula [40] (30). Methyl-3,5,6-trifluorobenzyl(1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compounds of the invention) C3) 14mg:

[化40]。[化40] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例23：本發明化合物I3的製造 將吡啶(130mg、1.65mmol)、(1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙甲醯氯(250mg、0.47mmol)及4-二甲胺基吡啶(3mg)依次加到2-氯-4-甲氧基甲基-3,5,6-三氟苯甲醇(56mg、0.23mmol)的四氫呋喃溶液(5mL)。在室溫下攪拌18小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化41](31)表示的2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物I3)42mg：Production Example 23: Production of Compound I3 of the Present Invention Pyridine (130 mg, 1.65 mmol), (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethyl ring Propargyl chloride (250 mg, 0.47 mmol) and 4-dimethylaminopyridine (3 mg) were added sequentially to 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (56 mg, 0.23). Methyl) in tetrahydrofuran (5 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. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure. The residue was applied to a silica gel column chromatography to give 2-chloro-4-methoxy group represented by the following formula [41] (31). Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate (this Inventive Compound I3) 42mg:

[化41]。[化41] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例24：本發明化合物P3的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(80mg、0.42mmol)及4-二甲胺基吡啶(3mg)加到2-氯-4-甲氧基甲基-3,5,6-三氟苯甲醇(67mg、0.28mmol)及(1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷甲酸(關於雙鍵的異構物的比率：Z/E=約8/1)(64mg、0.42mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌22小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化42](32)表示的2-氯-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物P3)(關於雙鍵的異構物的比率：Z/E=約8/1)25mg：Production Example 24: Production of Compound P3 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (80 mg, 0.42 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (67 mg, 0.28 mmol) and (1R)-trans-3-(1-propenyl)-2 , a solution of 2-dimethylcyclopropanecarboxylic acid (ratio of the isomer of the double bond: Z/E = about 8/1) (64 mg, 0.42 mmol) in chloroform (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methoxy group represented by the following formula [42] (32). Methyl-3,5,6-trifluorobenzyl(1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compound P3 of the invention) The ratio of isomers of the bond: Z/E = about 8/1) 25 mg:

[化42]。[化42] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.14(s，3H，Z+E體)、1.28(s，3H，Z+E體)、1.45(d，1H，Z+E體)、1.70(dd，3H，Z+E體)、2.18(m，1H，Z+E體)、3.40(s，3H，Z+E體)、4.58(m，2H，Z+E體)、5.11(m，1H，Z+E體)、5.29(m，2H，Z+E體)、5.60(m，1H，Z+E體)Colorless liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.14 (s, 3H, Z+E), 1.28 (s, 3H, Z+E), 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)

製造例25：本發明化合物W3的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(60mg、0.32mmol)及4-二甲胺基吡啶(3mg)加到2-氯-4-甲氧基甲基-3,5,6-三氟苯甲醇(50mg、0.21mmol)及2,2,3,3-四甲基環丙烷甲酸(45mg、0.32mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌24小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化43](33)表示的2-氯-4-甲氧基甲基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯(本發明化合物W3)52mg：Production Example 25: Production of Compound W3 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (60 mg, 0.32 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-chloro-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (50 mg, 0.21 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (45 mg, 0.32 mmol) of chloroform solution (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methoxy group represented by the following formula [43] (33). Methyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (Compound W3 of the invention) 52 mg:

[化43]。[化43] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.17(s，7H)、1.25(s，6H)、3.40(s，3H)、4.58(m，2H) 、5.29(m，2H)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)

製造例26：本發明化合物C4的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(67mg、0.35mmol)及4-二甲胺基吡啶(4mg)加到2-氯-4-乙炔基-3,5,6-三氟苯甲醇(65mg、0.29mmol)及(1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷甲酸(59mg、0.35mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌17小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化44](34)表示的2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物C4)45mg：Production Example 26: Production of Compound C4 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (67 mg, 0.35 mmol) and 4-dimethylaminopyridine ( 4 mg) was added to 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl alcohol (65 mg, 0.29 mmol) and (1R)-trans-3-(2-methyl-1-propenyl) -2,2-Dimethylcyclopropanecarboxylic acid (59 mg, 0.35 mmol) in chloroform (3 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-ethynyl group represented by the following formula [44] (34). 3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compound C4 of the invention) 45 mg :

[化44]。[化44] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例27：本發明化合物I4的製造 將吡啶(100mg、1.27mmol)、(1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙甲醯氯(191mg、0.36mmol)及4-二甲胺基吡啶(3mg)依次加到2-氯-4-乙炔基-3,5,6-三氟苯甲醇(40mg、0.18mmol)的四氫呋喃溶液(3mL)。在室溫下攪拌19小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化45](35)表示的2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物I4)32mg：Production Example 27: Production of Compound I4 of the Present Invention Pyridine (100 mg, 1.27 mmol), (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethyl ring Propargyl chloride (191 mg, 0.36 mmol) and 4-dimethylaminopyridine (3 mg) were added sequentially to 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl alcohol (40 mg, 0.18 mmol). Tetrahydrofuran 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-ethynyl group represented by the following formula [35] (35). 3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate (Compound I4 of the invention) ) 32mg:

[化45]。[化45] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例28：本發明化合物P4的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(50mg、0.26mmol)及4-二甲胺基吡啶(3mg)加到2-氯-4-乙炔基-3,5,6-三氟苯甲醇(48mg、0.22mmol)及(1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷甲酸(關於雙鍵的異構物的比率：Z/E=約8/1)(40mg、0.26mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌23小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化46](36)表示的2-氯-4-乙炔基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物P4)(關於雙鍵的異構物的比率：Z/E=約8/1)36mg：Production Example 28: Production of Compound P4 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (50 mg, 0.26 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl alcohol (48 mg, 0.22 mmol) and (1R)-trans-3-(1-propenyl)-2,2- A solution of dimethylcyclopropanecarboxylic acid (ratio of the isomer of the double bond: Z/E = about 8/1) (40 mg, 0.26 mmol) in chloroform (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-ethynyl group represented by the following formula [46] (36). 3,5,6-trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compound P4 of the invention) (depending on the double bond) Structure ratio: Z/E = about 8/1) 36 mg:

[化46]。[Chem. 46] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.12(s，3H，Z+E體)、1.27(s，3H，Z+E體)、1.45(d，1H，Z+E體)、1.79(dd，3H，Z+E體)、2.16(m，1H，Z+E體)、3.66(s，1H，Z+E體)、5.11(m，1H，Z+E體)、5.26(m，2H，Z+E體)、5.58(m，1H，Z+E體)Colorless liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.12 (s, 3H, Z+E), 1.27 (s, 3H, Z+E), 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)

製造例29：本發明化合物W4的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(46mg、0.24mmol)及4-二甲胺基吡啶(3mg)加到2-氯-4-乙炔基-3,5,6-三氟苯甲醇(45mg、0.20mmol)及2,2,3,3-四甲基環丙烷甲酸(34mg、0.24mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌25小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化47](37)表示的2-氯-4-乙炔基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯(本發明化合物W4)28mg：Production Example 29: Production of Compound W4 of the Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (46 mg, 0.24 mmol) and 4-dimethylaminopyridine ( 3 mg) to 2-chloro-4-ethynyl-3,5,6-trifluorobenzyl alcohol (45 mg, 0.20 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (34 mg, 0.24 mmol) A solution of 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-ethynyl group represented by the following formula [47] (37). 3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (Compound W4 of the invention) 28 mg:

[化47]。[化47] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.18(s，7H)、1.26(s，6H)、3.66(s，1H)、5.23(m，2H)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)

製造例30：本發明化合物M2的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(55mg、0.286mmol)及4-二甲胺基吡啶(5mg)加到2-氯-4-甲基-3,5,6-三氟苯甲醇(40mg、0.190mmol)及(1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷甲酸(46mg、0.190mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌17小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化48](38)表示的2-氯-4-甲基-3,5,6-三氟苄基 (1RS)-順式-3-[(Z)-2-氯-3,3,3-三氟-1-丙烯基]-2,2-二甲基環丙烷羧酸酯(本發明化合物M2)63mg：Production Example 30: Production of Compound M2 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (55 mg, 0.286 mmol) and 4-dimethylaminopyridine ( 5 mg) was added to 2-chloro-4-methyl-3,5,6-trifluorobenzyl alcohol (40 mg, 0.190 mmol) and (1RS)-cis-3-[(Z)-2-chloro-3, A solution of 3,3-trifluoro-1-propenyl]-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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-chloro-4-methyl- represented by the following formula [48] (38). 3,5,6-trifluorobenzyl (1RS)-cis-3-[(Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethyl Cyclopropanecarboxylate (Compound M2 of the invention) 63 mg:

[化48]。[48] .

無色液體：1 H-NMR(CDCl3 ，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)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)

其次，顯示製劑例。此外，份是表示質量份。Next, a formulation example is shown. In addition, the serving is a part by mass.

製劑例1 將本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各0.1份溶解於二甲苯(xylene)10份，將其混合於脫臭煤油89.9份，得到油劑。Formulation Example 1 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 part was dissolved in 10 parts of xylene, and this was mixed with 89.9 parts of deodorized kerosene to obtain an oil agent.

製劑例2 將混合溶解了本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各0.1份及脫臭煤油39.9份之物填充於噴霧罐(aerosol)容器，安裝了閥部分後，經由該閥部分加壓填充噴射劑(液化石油氣)60份，得到油性噴霧罐。Formulation Example 2 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 0.1 part of each of W4 and 39.9 parts of deodorized kerosene were filled in an aerosol container, and after the valve portion was attached, 60 parts of the propellant (liquefied petroleum gas) was pressurized and filled through the valve portion to obtain an oily spray can.

製劑例3 將混合溶解了本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各0.6份、二甲苯5份、脫臭煤油3.4份及RHEODOL MO-60(乳化劑，花王股份有限公司註冊商標)1份之物，與水50份填充於噴霧罐容器，經由閥部分加壓填充噴射劑(液化石油氣)40份，得到水性噴霧罐。Formulation Example 3 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 0.6 parts of W4, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of RHEODOL MO-60 (emulsifier, registered trademark of Kao Co., Ltd.), 50 parts of water and 50 parts of water are filled in the spray can container, through the valve part 40 parts of a pressurized filling propellant (liquefied petroleum gas) was obtained to obtain an aqueous spray can.

製劑例4 將本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各0.3g及BHT0.5g均勻攪拌混合於蚊香用基材(混合了除蟲菊萃取糟粉、木粉、紅楠粉及澱粉之物)99.2g後，將加入包含作為著色劑的孔雀綠(malachite green)的水100mL，充分混練後之物成型乾燥，得到蚊香。Formulation Example 4 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 0.3g and BHT0.5g are uniformly stirred and mixed in the mosquito-repellent substrate (mixed with pyrethrum extract powder, wood powder, red lotus powder and starch) 99.2g, and then malachite green (malachite) is added as a coloring agent. 100 mL of water of green), and the mixture was thoroughly molded and dried to obtain mosquito coils.

製劑例5 將脫臭煤油加到本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各0.8g、胡椒基丁醚(piperonyl butoxide)0.4g及染料並溶解，全部以10mL。將該溶液0.5mL均勻含浸於22mm×35mm、厚度2.8mm的蚊香片用基材(將棉籽絨與紙漿的混合物的原纖維凝固成板狀者)，得到蚊香片劑。Formulation Example 5 Deodorized kerosene is added to the compounds C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, C3, I3, P3, W3, C4, I4, 0.8 g of each of P4 and W4, 0.4 g of piperonyl butoxide and a dye were dissolved, and all were 10 mL. 0.5 mL of this solution was uniformly impregnated into a substrate for a mosquito-repellent sheet of 22 mm × 35 mm and a thickness of 2.8 mm (the fibrils of a mixture of cotton linter and pulp were solidified into a plate shape) to obtain a mosquito-repellent tablet.

製劑例6 將本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各0.7份及BHT0.3份溶解於界面活性劑(二乙二醇單丁醚)50份與淨化水(purified water)49份而得的液劑放入聚酯製容器，藉由***能以加熱器(heater)將上部加熱的吸液芯(將無機粉體燒成者)，得到加熱蒸散裝置所使用的水性蚊香液劑。Formulation Example 6 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 0.7 parts and 0.3 parts of BHT dissolved in 50 parts of surfactant (diethylene glycol monobutyl ether) and 49 parts of purified water are placed in a polyester container, which can be heated by insertion. A heater that heats the upper portion (the inorganic powder is fired) to obtain an aqueous mosquito liquid solution used in the heating and squirting device.

製劑例7 將本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各3.0份、惡蟲酮3.0份及偶氮二甲醯胺94.0份充分混合後，將其20g填充到塑膠膜(plastic film)袋，將其收納於耐熱容器並裝填點火器得到燻煙劑。Formulation Example 7 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 After 3.0 parts, 3.0 parts of triammonium ketone and 94.0 parts of azomethicamine were thoroughly mixed, 20 g of the mixture was filled in a plastic film bag, which was housed in a heat-resistant container and filled with an igniter to obtain a fumigation agent.

製劑例8 將本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各10mg溶解於適量的丙酮，均勻塗佈於5cm×5cm、厚度0.3mm的不織布後，將丙酮風乾，得到常溫揮散劑。Formulation Example 8 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 are each 10 mg was dissolved in an appropriate amount of acetone, and uniformly applied to a nonwoven fabric of 5 cm × 5 cm and a thickness of 0.3 mm, and then acetone was air-dried to obtain a room temperature dispersing agent.

製劑例9 將本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，C3，I3，P3，W3，C4，I4，P4及W4的各10份、包含聚氧乙烯烷基醚硫酸銨鹽(polyoxyethylene alkyl ether sulfate ammonium salt)50份的白碳(white carbon)35份及水55份混合，藉由以濕式粉碎法進行微粉碎，得到10%流動劑。Formulation Example 9 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 are each 10 parts, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt and 55 parts of water were mixed and finely pulverized by wet pulverization method. 10% flow agent.

其次，顯示以本發明化合物作為有害生物防除劑的有效成分有效當作試驗例。Next, it is shown that the active ingredient of the compound of the present invention as a pest control agent is effectively used as a test example.

效果試驗例1(使用淡色庫蚊的接觸試驗) 將包含0.1mg的本發明化合物C1，I1，P1，R1，T1，W1，C4，I4，P4及W4的0.2%丙酮溶液0.05mL滴下到直徑28mm、內高13mm、底面積6.15cm2 之培養皿(petri dish)，均勻地擴展於底面後，以二連球去除丙酮。將淡色庫蚊的雌6隻放入各試樣被保持於底面的培養皿，以開孔的膜覆蓋上側後，每1分記錄擊倒(knock-down)數，測定且記錄了KT50 (50%擊倒的時間)與24小時後的致死率。關於就擊倒率顯示規定以上的數值的試樣係更將丙酮加到前述0.2%丙酮溶液稀釋成10倍，當作0.02%丙酮溶液，依次重複了前述的各器具(培養皿)、試驗方法。 而且，作為比較對照使用胺菊酯：1,3,4,5,6,7-六氫-1,3-二氧代-2H-異吲哚-2-基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(以下記為比較化合物A)，同樣地進行了試驗。 將結果顯示於表1Effect Test Example 1 (contact test using Culex pipiens pallens) 0.05 mL of a 0.2% acetone solution containing 0.1 mg of the compound of the present invention C1, I1, P1, R1, T1, W1, C4, I4, P4 and W4 was dropped to a diameter A petri dish of 28 mm, an inner height of 13 mm, and a bottom area of 6.15 cm 2 was uniformly spread over the bottom surface, and acetone was removed by two balls. Six females of Culex pipiens pallens were placed in a petri dish in which each sample was held on the bottom surface, and the upper side was covered with an open-cell membrane. The number of knock-downs was recorded every one minute, and KT 50 was measured and recorded. 50% knockdown time) and lethality after 24 hours. Regarding the sample in which the above-mentioned numerical value is specified as the knockdown rate, the acetone is added to the above-mentioned 0.2% acetone solution and diluted to 10 times, and the above-mentioned respective instruments (culture dishes) and test methods are sequentially repeated as a 0.02% acetone solution. . Moreover, as a comparative control, the use of methrin: 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-dimethylcyclopropanecarboxylate (hereinafter referred to as Comparative Compound A) was tested in the same manner. The results are shown in Table 1.

【表1】 【Table 1】

試驗的結果得知本發明化合物C1，I1，P1，R1，T1，W1，C4，I4，P4及W4都顯示超過比較化合物A(胺菊酯)之高的擊倒率(knock-down activity)。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 the comparative compound A (methrin). .

效果試驗例2(使用淡色庫蚊的接觸試驗) 將包含0.1mg的本發明化合物C2，I2，P2，R2，T2，W2，C3，I3，P3及W3的0.2%丙酮溶液0.05mL滴下到直徑28mm、內高13mm、底面積6.15cm2 之培養皿，均勻地擴展於底面後，以二連球去除丙酮。將淡色庫蚊的雌6隻放入各試樣被保持於底面的培養皿，以開孔的膜覆蓋上側後，每1分記錄擊倒數，測定且記錄了KT50 (50%擊倒的時間)與24小時後的致死率。關於就擊倒率顯示規定以上的數值的試樣係更將丙酮加到前述0.2%丙酮溶液稀釋成10倍，當作0.02%丙酮溶液，依次重複了前述的各器具(培養皿)、試驗方法。 而且，作為比較對照使用胺菊酯：1,3,4,5,6,7-六氫-1,3-二氧代-2H-異吲哚-2-基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(以下記為比較化合物A)，同樣地進行了試驗。 將結果顯示於表2Effect Test Example 2 (contact test using Culex pipiens pallens) 0.05 mL of a 0.2% acetone solution containing 0.1 mg of the compound of the present invention C2, I2, P2, R2, T2, W2, C3, I3, P3 and W3 was dropped to a diameter A petri dish of 28 mm, an inner height of 13 mm, and a bottom area of 6.15 cm 2 was uniformly spread over the bottom surface, and acetone was removed by two balls. Six females of Culex pipiens pallens were placed in a petri dish with each sample held on the bottom surface, and the upper side was covered with an open-cell membrane. The number of knockdowns was recorded every 1 minute, and KT 50 was measured and recorded (50% knockdown Time) and lethality after 24 hours. Regarding the sample in which the above-mentioned numerical value is specified as the knockdown rate, the acetone is added to the above-mentioned 0.2% acetone solution and diluted to 10 times, and the above-mentioned respective instruments (culture dishes) and test methods are sequentially repeated as a 0.02% acetone solution. . Moreover, as a comparative control, the use of methrin: 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-dimethylcyclopropanecarboxylate (hereinafter referred to as Comparative Compound A) was tested in the same manner. The results are shown in Table 2.

【表2】 【Table 2】

試驗的結果得知本發明化合物C2，I2，P2，R2，T2，W2，C3，I3，P3及W3都顯示超過比較化合物A(胺菊酯)之高的擊倒率。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 showed a higher knockdown rate than the comparative compound A (methrin).

效果試驗例3(使用淡色庫蚊的常溫揮散性試驗) 將淡色庫蚊的雌10隻放入直徑9cm、內高1.9cm、底面積63.6cm2 之培養皿，以16網目的金屬絲網覆蓋。將包含0.09mg的所調製的藥劑的本發明化合物I1，P1，W1，I2，P2，W2，I3，P3，W3，P4及W4的2%丙酮溶液0.5mL滴下到相同尺寸的培養皿(直徑9cm、內高1.9cm、底面積63.6cm2 )，將丙酮風乾。接著，將塗佈了該藥劑的培養皿倒置於上述金屬絲網之上。然後每1分調查擊倒的淡色庫蚊雌成蟲的數，求擊倒率。 而且，作為比較對照使用以下列的式[化49](39)表示的2-氯-6-氟苄基 2,2,3,3-四甲基環丙烷羧酸酯(日本國特開昭57-165343號公報所記載的化合物。以下記為比較化合物B)及益避寧：(RS)-(EZ)-1-乙炔基-2-甲基-2-戊烯基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(以下記為比較化合物C)，同樣地進行了試驗。Effect Test Example 3 (Normal temperature volatility test using Culex pipiens pallens) The female 10 of Culex pipiens pallens was placed in a petri dish having a diameter of 9 cm, an inner height of 1.9 cm, and a bottom area of 63.6 cm 2 , and covered with a wire mesh of 16 mesh. . 0.5 mL of a 2% acetone solution of the present compound I1, P1, W1, I2, P2, W2, I3, P3, W3, P4 and W4 containing 0.09 mg of the prepared medicament was dropped into a Petri dish of the same size (diameter 9 cm, inner height 1.9 cm, bottom area 63.6 cm 2 ), acetone was air-dried. Next, the petri dish coated with the drug was poured on the above-mentioned wire mesh. Then, the number of female adults of Culex pipiens pallens was knocked down every 1 minute to find the knockdown rate. Further, as a comparative control, 2-chloro-6-fluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate represented by the following formula [Chem. 49] (39) was used (Japanese Special Opening) Compounds described in JP-A-57-165343. Hereinafter, it is referred to as Comparative Compound B) and Yishunning: (RS)-(EZ)-1-ethynyl-2-methyl-2-pentenyl (1R)-inverse The cis-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as Comparative Compound C) was tested in the same manner.

[化49]將其結果顯示於表3[化49] The results are shown in Table 3.

【表3】 【table 3】

試驗的結果得知本發明化合物之I1，P1，W1，I2，P2，W2，I3，P3，W3，P4及W4都顯示超過比較化合物B及比較化合物C(益避寧)之高的擊倒率。As a result of the test, it was found that I1, P1, W1, I2, P2, W2, I3, P3, W3, P4 and W4 of the compound of the present invention all showed a knockdown higher than that of Comparative Compound B and Comparative Compound C (Yi Ning). rate.

效果試驗例4(利用蚊香進行的殺蟲試驗) 將淡色庫蚊成蟲約50隻釋放到70cm立方的玻璃箱(glass chamber)內，將電池式小型風扇(葉片的直徑13cm)設置於箱內使其旋轉。一將藉由製劑例4得到的本發明化合物C1，I1，P1，R1，T1，C2，I2，M2，P2，R2，C3，I3，P3，C4及I4的蚊香0.1g的兩端點火後放入玻璃箱，在15分以內就能使80%以上的淡色庫蚊擊倒，在翌日就能使其80%以上致死。Effect Test Example 4 (Insecticide test using mosquito coil) About 50 adult Culex pipiens pallens were released into a 70 cm cubic glass chamber, and a small battery type fan (leaf diameter of 13 cm) was placed in the box. Its rotation. After igniting both ends of the compound of the present invention C1, I1, P1, R1, T1, C2, I2, M2, P2, R2, C3, I3, P3, C4 and I4 obtained by Formulation Example 4 Put it in a glass box and knock down more than 80% of Culex pipiens in less than 15 minutes, killing more than 80% on the next day.

效果試驗例5(利用燻煙劑進行的殺蟲試驗) 在6榻榻米的房間使用加熱器將比照製劑例7調製的本發明化合物C1，I1，P1，R1，T1，C2，I2，M2，P2，R2，T2，C3，I3，P3，C4，I4及P4的燻煙劑1袋加熱到約250℃的結果，成分由以塑膠膜形成的噴煙孔擴散到房間全體，對以蟑螂、蚤、臭蟲為首，以及室塵蟎或腐食酪蟎等的家塵蟎(house-dust mites)類的防除也有效。Effect Test Example 5 (Insecticidal test by fumigation agent) The compound of the present invention C1, I1, P1, R1, T1, C2, I2, M2, P2 prepared in accordance with Formulation Example 7 was used in a room of 6 tatami using a heater. , the R2, T2, C3, I3, P3, C4, I4 and P4 fumigation agents were heated to about 250 ° C. The components were diffused into the room by the puff holes formed by the plastic film. It is also effective in the prevention of the house-dust mites such as house dust mites or rot.

效果試驗例6(利用噴霧罐進行的殺蟲試驗) 將家蠅雌成蟲約30隻釋放到60cm立方的玻璃箱內，由箱子的側壁的孔每一秒鐘將藉由製劑例2得到的本發明化合物C1，I1，P1，R1，T1，W1，C2，I2，M2，P2，R2，T2，W2，I3，P3，I4及P4的噴霧罐噴霧。其結果，在2分以內能使100%的家蠅擊倒，認定了本發明化合物具有高的擊倒效果。Effect Test Example 6 (Insecticidal Test by Spray Can) About 30 female adults of Musca domestica were released into a 60 cm cubic glass box, and the hole obtained from the side wall of the box was obtained by Formulation Example 2 per second. Spray tank sprays of the inventive compounds C1, I1, P1, R1, T1, W1, C2, I2, M2, P2, R2, T2, W2, I3, P3, I4 and P4. As a result, 100% of the housefly was knocked down within 2 minutes, and it was confirmed that the compound of the present invention has a high knocking effect.

＜含Br酯化合物的實施例＞ 顯示本發明化合物(含Br酯化合物)的製造例。<Example of Br-containing ester compound> A production example of the compound of the present invention (containing a Br ester compound) is shown.

製造例1：化合物(X)的製造 在室溫下將溴化四丁銨(1440mg、4.47mmol)、樟腦磺酸(624mg、2.69mmol)、亞硝酸鈉(186mg、2.69mmol)、二價溴化銅(5mg、0.02mmol)依次添加到甲基 2-胺基-3,5,6-三氟苯甲酸酯(558mg、2.72mmol)的乙腈(25mL)溶液。在60℃下攪拌24小時後，在室溫下將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化50](X)表示的甲基 2-溴-3,5,6-三氟苯甲酸酯340mg：Production Example 1: Production of Compound (X) Tetrabutylammonium bromide (1440 mg, 4.47 mmol), camphorsulfonic acid (624 mg, 2.69 mmol), sodium nitrite (186 mg, 2.69 mmol), divalent bromine at room temperature Copper (5 mg, 0.02 mmol) was added to 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 solution at room temperature, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain methyl 2-bromo-3,5 represented by the following formula [50] (X). , 6-trifluorobenzoate 340mg:

[化50]。[化50] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：4.00(s，3H)、7.16(m，1H)Colorless liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 4.00 (s, 3H), 7.16 (m, 1H)

製造例2：化合物(XI)的製造 在冰冷下將二異丁基氫化鋁(1.5M 甲苯溶液、2.8mL、4.19mmol)滴下到甲基 2-溴-3,5,6-三氟苯甲酸酯(340mg、1.27mmol)的甲苯(4mL)及四氫呋喃(4mL)的混合溶液。在冰冷下攪拌2小時後，將反應液注加到1N鹽酸水溶液及水，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化51](XI)表示的2-溴-3,5,6-三氟苯甲醇262mg：Production Example 2: Production of Compound (XI) Diisobutylaluminum hydride (1.5 M solution in toluene, 2.8 mL, 4.19 mmol) was added dropwise to methyl 2-bromo-3,5,6-trifluorobenzene under ice cooling. A mixed solution of an acid ester (340 mg, 1.27 mmol) in toluene (4 mL) and tetrahydrofuran (4 mL). After stirring for 2 hours under ice cooling, the reaction mixture was poured into 1N aqueous hydrochloric acid and water, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain 2-bromo-3,5,6 represented by the following formula [Chem. 51] (XI). -trifluorobenzyl alcohol 262mg:

[化51]。[化51] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.04(t，1H)、4.85(dd，2H)、7.04(m，1H)White solid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 2.04 (t, 1H), 4.85 (dd, 2H), 7.04 (m, 1H)

製造例3：化合物(XII)的製造 在室溫下將三乙胺(1.9mL、13.65mmol)、苯甲胺(1.00g、9.33mmol)依次滴下到甲基 4-甲基-2,3,5,6-四氟苯甲酸酯(1.01g、4.55mmol)的甲苯(15mL)溶液。在100℃下攪拌10小時後，將水注加到反應液，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化52](XII)表示的甲基 2-苄胺基-4-甲基-3,5,6-三氟苯甲酸酯1.18g：Production Example 3: Production of Compound (XII) Triethylamine (1.9 mL, 13.65 mmol) and benzylamine (1.00 g, 9.33 mmol) were successively dropped to methyl 4-methyl-2,3 at room temperature. A solution of 5,6-tetrafluorobenzoate (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. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain methyl 2-benzylamino-4 as the formula (52) (XII). -Methyl-3,5,6-trifluorobenzoate 1.18g:

[化52]。[化52] .

黃色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.21(m，3H)、3.88(s，3H)、4.50(m，2H)、6.96(brs，1H)、7.29(m，5H)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)

製造例4：化合物(XIII)的製造 在室溫下將鈀碳(117mg)注加到甲基 2-苄胺基-4-甲基-3,5,6-三氟苯甲酸酯(1.15g、3.72mmol)的乙酸乙酯(50mL)溶液，在氫環境下取代反應液。在氫環境下在室溫下攪拌3小時後，對反應液進行矽藻土過濾後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化53](XIII)表示的甲基 2-胺基-4-甲基-3,5,6-三氟苯甲酸酯690mg：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) at room temperature. A solution of g, 3.72 mmol) in ethyl acetate (50 mL) was evaporated in vacuo. After stirring at room temperature for 3 hours in a hydrogen atmosphere, the reaction liquid was filtered through celite, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain the following formula (53). Methyl 2-amino-4-methyl-3,5,6-trifluorobenzoate 690 mg represented by XIII):

[化53]。[化53] .

黃色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.24(m，3H)、3.92(s，3H)、5.55(brs，2H)Yellow liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 2.24 (m, 3H), 3.92 (s, 3H), 5.55 (brs, 2H)

製造例5：化合物(XIV)的製造 在室溫下將溴化四丁銨(1867mg、5.80mmol)、樟腦磺酸(809mg、3.49mmol)、亞硝酸鈉(290mg、4.20mmol)、二價溴化銅(18mg、0.08mmol)依次添加到甲基 2-胺基-4-甲基-3,5,6-三氟苯甲酸酯(637mg、2.91mmol)的乙腈(30mL)溶液。在60℃下攪拌24小時後，在室溫下將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化54](XIV)表示的甲基 2-溴-4-甲基-3,5,6-三氟苯甲酸酯354mg：Production Example 5: Production of Compound (XIV) Tetrabutylammonium bromide (1867 mg, 5.80 mmol), camphorsulfonic acid (809 mg, 3.49 mmol), sodium nitrite (290 mg, 4.20 mmol), divalent bromine at room temperature Copper (18 mg, 0.08 mmol) was added to 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 solution at room temperature, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain methyl 2-bromo-4-methyl represented by the following formula [54] (XIV). Base-3,5,6-trifluorobenzoate 354mg:

[化54]。[54] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.30(m，3H)、3.98(s，3H)Colorless liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 2.30 (m, 3H), 3.98 (s, 3H)

製造例6：化合物(XV)的製造 在冰冷下將二異丁基氫化鋁(1.5M 甲苯溶液、2.5mL、3.75mmol)滴下到甲基 2-溴-4-甲基-3,5,6-三氟苯甲酸酯(354mg、1.25mmol)的甲苯(3mL)及四氫呋喃(3mL)的混合溶液。在冰冷下攪拌2小時後，將反應液注加到1N鹽酸水溶液及水，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化55](XV)表示的2-溴-4-甲基-3,5,6-三氟苯甲醇278mg：Production Example 6: Production of Compound (XV) Diisobutylaluminum hydride (1.5 M toluene solution, 2.5 mL, 3.75 mmol) was added dropwise to methyl 2-bromo-4-methyl-3,5,6 under ice cooling. A mixed solution of trifluorobenzoic acid ester (354 mg, 1.25 mmol) in toluene (3 mL) and tetrahydrofuran (3 mL). After stirring for 2 hours under ice cooling, the reaction mixture was poured into 1N aqueous hydrochloric acid and water, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-4-methyl- represented by the following formula [5] (XV). 3,5,6-trifluorobenzyl alcohol 278mg:

[化55]。[化55] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.05(t，1H)、2.28(m，3H)、4.86(dd，2H)White solid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 2.05 (t, 1H), 2.28 (m, 3H), 4.86 (dd, 2H)

製造例7：化合物(XVI)的製造 在室溫下將三乙胺(3.4mL、24.53mmol)、苯甲胺(1.73g、16.14mmol)依次滴下到甲基 4-甲氧基甲基-2,3,5,6-四氟苯甲酸酯(2.03g、8.06mmol)的甲苯(20mL)溶液。在100℃下攪拌7小時後，將水注加到反應液，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化56](XVI)表示的甲基 2-苄胺基-4-甲氧基甲基-3,5,6-三氟苯甲酸酯2.32g：Production Example 7: Production of Compound (XVI) Triethylamine (3.4 mL, 24.53 mmol) and benzylamine (1.73 g, 16.14 mmol) were successively dropped to methyl 4-methoxymethyl-2 at room temperature. , a solution of 3,5,6-tetrafluorobenzoate (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give methyl 2-benzylamino-4 as the formula (5). -Methoxymethyl-3,5,6-trifluorobenzoate 2.32g:

[化56]。[化56] .

黃色液體：1 H-NMR(CDCl3 ，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)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)

製造例8：化合物(XVII)的製造 在室溫下將鈀碳(230mg)注加到甲基 2-苄胺基-4-甲氧基甲基-3,5,6-三氟苯甲酸酯(2.32g、6.84mmol)的乙酸乙酯(80mL)溶液，在氫環境下取代反應液。在氫環境下在室溫下攪拌3小時後，對反應液進行矽藻土過濾後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化57](XVII)表示的甲基 2-胺基-4-甲氧基甲基-3,5,6-三氟苯甲酸酯1.12g：Production Example 8: Production of Compound (XVII) Palladium carbon (230 mg) was added to methyl 2-benzylamino-4-methoxymethyl-3,5,6-trifluorobenzoic acid at room temperature. A solution of the ester (2.32 g, 6.84 mmol) in ethyl acetate (80 mL) was evaporated in vacuo. After stirring at room temperature for 3 hours in a hydrogen atmosphere, the reaction mixture was filtered through Celite, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give the following formula (57). Methyl 2-amino-4-methoxymethyl-3,5,6-trifluorobenzoate represented by XVII) 1.12 g:

[化57]。[化57] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：3.40(s，3H)、3.94(s，3H)、4.56(m，2H)、5.59(brs，2H)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)

製造例9：化合物(XVIII)的製造 在室溫下將溴化四丁銨(811mg、2.52mmol)、樟腦磺酸(351mg、1.51mmol)、亞硝酸鈉(104mg、1.51mmol)、二價溴化銅(5mg、0.02mmol)依次添加到甲基 2-胺基-4-甲氧基甲基-3,5,6-三氟苯甲酸酯(314mg、1.26mmol)的乙腈(15mL)溶液。在60℃下攪拌24小時後，在室溫下將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化58](XVIII)表示的甲基 2-溴-4-甲氧基甲基-3,5,6-三氟苯甲酸酯121mg：Production Example 9: Production of Compound (XVIII) Tetrabutylammonium bromide (811 mg, 2.52 mmol), camphorsulfonic acid (351 mg, 1.51 mmol), sodium nitrite (104 mg, 1.51 mmol), divalent bromine at room temperature Copper (5 mg, 0.02 mmol) was added to 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 solution at room temperature, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied 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 121 mg:

[化58]。[化58] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：3.39(s，3H)、4.00(s，3H)、4.59(m，2H)Colorless liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 3.39 (s, 3H), 4.00 (s, 3H), 4.59 (m, 2H)

製造例10：化合物(XIX)的製造 在冰冷下將二異丁基氫化鋁(1.5M 甲苯溶液、0.8mL、1.20mmol)滴下到甲基 2-溴-4-甲氧基甲基-3,5,6-三氟苯甲酸酯(121mg、0.39mmol)的甲苯(2mL)及四氫呋喃(2mL)的混合溶液。在冰冷下攪拌2小時後，將反應液注加到1N鹽酸水溶液及水，以乙酸乙酯進行了萃取。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化59](XIX)表示的2-溴-4-甲氧基甲基-3,5,6-三氟苯甲醇69mg：Production Example 10: Production of Compound (XIX) Diisobutylaluminum hydride (1.5 M toluene solution, 0.8 mL, 1.20 mmol) was added dropwise to methyl 2-bromo-4-methoxymethyl-3 under ice cooling. A mixed solution of 5,6-trifluorobenzoate (121 mg, 0.39 mmol) in toluene (2 mL) and tetrahydrofuran (2 mL). After stirring for 2 hours under ice cooling, the reaction mixture was poured into 1N aqueous hydrochloric acid and water, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-4-methoxy group represented by the following formula [59] (XIX). Methyl-3,5,6-trifluorobenzyl alcohol 69mg:

[化59]。[化59] .

白色固體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：2.08(t，1H)、3.39(s，3H)、4.58(m，2H)、4.89(dd，2H)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)

製造例11：本發明化合物3的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(59mg、0.31mmol)及4-二甲胺基吡啶(2mg)加到2-溴-3,5,6-三氟苯甲醇(49mg、0.20mmol)及(1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷甲酸(51mg、0.30mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌19小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化60](XX)表示的2-溴-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物3)17mg：Production Example 11: Production of Compound 3 of the Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (59 mg, 0.31 mmol) and 4-dimethylaminopyridine ( 2 mg) to 2-bromo-3,5,6-trifluorobenzyl alcohol (49 mg, 0.20 mmol) and (1R)-trans-3-(2-methyl-1-propenyl)-2,2- A solution of dimethylcyclopropanecarboxylic acid (51 mg, 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to obtain 2-bromo-3,5,6 represented by the following formula [60] (XX). -trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Compound 3 of the invention) 17 mg:

[化60]。[60] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例12：本發明化合物9的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(91mg、0.47mmol)及4-二甲胺基吡啶(3mg)加到2-溴-3,5,6-三氟苯甲醇(88mg、0.37mmol)及(1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷甲酸(99mg、0.48mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌18小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化61](XXI)表示的2-溴-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物9)118mg：Production Example 12: Production of Compound 9 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (91 mg, 0.47 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-bromo-3,5,6-trifluorobenzyl alcohol (88 mg, 0.37 mmol) and (1R)-trans-3-(2,2-dichloro-1-vinyl)-2. A solution of 2-dimethylcyclopropanecarboxylic acid (99 mg, 0.48 mmol) in chloroform (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-3,5,6 represented by the following formula [X. -trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate (Compound 9 of the invention) 118 mg:

[化61]。[化61] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例13：本發明化合物16的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(50mg、0.26mmol)及4-二甲胺基吡啶(3mg)加到2-溴-3,5,6-三氟苯甲醇(41mg、0.17mmol)及(1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷甲酸(關於雙鍵的異構物的比率：Z/E=約8/1)(40mg、0.26mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌24小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化62](XXII)表示的2-溴-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物16)(關於雙鍵的異構物的比率：Z/E=約8/1)32mg：Production Example 13: Production of Compound 16 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (50 mg, 0.26 mmol) and 4-dimethylaminopyridine ( 3 mg) to 2-bromo-3,5,6-trifluorobenzyl alcohol (41 mg, 0.17 mmol) and (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropane A solution of formic acid (ratio of the isomer of the double bond: Z/E = about 8/1) (40 mg, 0.26 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-3,5,6, which is represented by the following formula [62] (XXII). -Trifluorobenzyl (1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Compound 16 of the invention) (ratio of isomers with respect to double bonds: Z/E=about 8/1) 32mg:

[化62]。[化62] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.12(s，3H，Z+E體)、1.27(s，3H，Z+E體)、1.46(d，1H，Z+E體)、1.71(dd，3H，Z+E體)、2.18(m，1H，Z+E體)、5.12(m，1H，Z+E體)、5.30(m，2H，Z+E體)、5.62(m，1H，Z+E體)、7.07(m，1H)Colorless liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.12 (s, 3H, Z+E), 1.27 (s, 3H, Z+E), 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)

製造例14：本發明化合物23的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(44mg、0.23mmol)及4-二甲胺基吡啶(3mg)加到2-溴-3,5,6-三氟苯甲醇(35mg、0.15mmol)及2,2,3,3-四甲基環丙烷甲酸(33mg、0.23mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌20小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化63](XXIII)表示的2-溴-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯(本發明化合物23)28mg：Production Example 14: Production of Compound 23 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (44 mg, 0.23 mmol) and 4-dimethylaminopyridine ( 3 mg) of 2-bromo-3,5,6-trifluorobenzyl alcohol (35 mg, 0.15 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (33 mg, 0.23 mmol) in chloroform (2mL). After stirring at room temperature for 20 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-3,5,6 represented by the following formula [Chem. 63] (XXIII). -trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (Compound 23 of the invention) 28 mg:

[化63]。[化63] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.17(s，7H)、1.25(s，6H)、5.32(m，2H)、7.06(m，1H)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)

製造例15：本發明化合物26的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(34mg、0.18mmol)及4-二甲胺基吡啶(2mg)加到2-溴-4-甲基-3,5,6-三氟苯甲醇(30mg、0.12mmol)及(1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷甲酸(30mg、0.18mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌20小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化64](XXIV)表示的2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物26)22mg：Production Example 15 Production of Compound 26 of the Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (34 mg, 0.18 mmol) and 4-dimethylaminopyridine ( 2 mg) to 2-bromo-4-methyl-3,5,6-trifluorobenzyl alcohol (30 mg, 0.12 mmol) and (1R)-trans-3-(2-methyl-1-propenyl) -2,2-Dimethylcyclopropanecarboxylic 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-4-methyl- represented by the following formula [V. 64] (XXIV). 3,5,6-trifluorobenzyl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Compound 26 of the invention) 22 mg :

[化64]。[化64] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例16：本發明化合物32的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(35mg、0.18mmol)及4-二甲胺基吡啶(3mg)加到2-溴-4-甲基-3,5,6-三氟苯甲醇(30mg、0.12mmol)及(1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷甲酸(37mg、0.18mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌16小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化65](XXV)表示的2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物32)35mg：Production Example 16: Production of Compound 32 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (35 mg, 0.18 mmol) and 4-dimethylaminopyridine ( 3 mg) added to 2-bromo-4-methyl-3,5,6-trifluorobenzyl alcohol (30 mg, 0.12 mmol) and (1R)-trans-3-(2,2-dichloro-1-ethylene A solution of 2,2-dimethylcyclopropanecarboxylic acid (37 mg, 0.18 mmol) in chloroform (2 mL). After stirring at room temperature for 16 hours, water was added to the reaction liquid, and the reaction liquid was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 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-dimethylcyclopropanecarboxylate (compound 32 of the invention) ) 35mg:

[化65]。[化65] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例17：本發明化合物39的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(82mg、0.43mmol)及4-二甲胺基吡啶(5mg)加到2-溴-4-甲基-3,5,6-三氟苯甲醇(84mg、0.33mmol)及(1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷甲酸(關於雙鍵的異構物的比率：Z/E=約8/1)(66mg、0.43mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌18小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化66](XXVI)表示的2-溴-4-甲基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物39)(關於雙鍵的異構物的比率：Z/E=約8/1)42mg：Production Example 17: Production of Compound 39 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (82 mg, 0.43 mmol) and 4-dimethylaminopyridine ( 5 mg) was added to 2-bromo-4-methyl-3,5,6-trifluorobenzyl alcohol (84 mg, 0.33 mmol) and (1R)-trans-3-(1-propenyl)-2,2- A solution of dimethylcyclopropanecarboxylic acid (ratio of the isomer of the double bond: Z/E = about 8/1) (66 mg, 0.43 mmol) in chloroform (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-4-methyl- represented by the following formula [? 66] (XXVI). 3,5,6-trifluorobenzyl(1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Compound 39 of the invention) (About the double bond) Structure ratio: Z/E = about 8/1) 42 mg:

[化66]。[化66] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.13(s，3H，Z+E體)、1.28(s，3H，Z+E體)、1.45(d，1H，Z+E體)、1.70(dd，3H，Z+E體)、2.18(m，1H，Z+E體)、2.29(m，3H，Z+E體)、5.12(m，1H，Z+E體)、5.28(m，2H，Z+E體)、5.59(m，1H，Z+E體)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)

製造例18：本發明化合物46的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(29mg、0.15mmol)及4-二甲胺基吡啶(3mg)加到2-溴-4-甲基-3,5,6-三氟苯甲醇(25mg、0.10mmol)及2,2,3,3-四甲基環丙烷甲酸(21mg、0.15mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌22小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化67](XXVII)表示的2-溴-4-甲基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯(本發明化合物46)18mg：Production Example 18: Production of Compound 46 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (29 mg, 0.15 mmol) and 4-dimethylaminopyridine ( 3 mg) to 2-bromo-4-methyl-3,5,6-trifluorobenzyl alcohol (25 mg, 0.10 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (21 mg, 0.15 mmol) A solution of 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. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure. The residue was applied to a silica gel column chromatography to give 2-bromo-4-methyl- represented by the following formula [Chem. 67] (XXVII). 3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (Compound 46 of the invention) 18 mg:

[化67]。[67] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.16(s，7H)、1.24(s，6H)、2.28(m，3H)、5.32(m，2H)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)

製造例19：本發明化合物49的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(70mg、0.36mmol)及4-二甲胺基吡啶(2mg)加到2-溴-4-甲氧基甲基-3,5,6-三氟苯甲醇(69mg、0.24mmol)及(1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷甲酸(80mg、0.48mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌23小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化68](XXVIII)表示的2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物49)17mg：Production Example 19: Production of Compound 49 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (70 mg, 0.36 mmol) and 4-dimethylaminopyridine ( 2 mg) to 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (69 mg, 0.24 mmol) and (1R)-trans-3-(2-methyl-1- A solution of propylene)-2,2-dimethylcyclopropanecarboxylic 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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-4-methoxy group represented by the following formula [68] (XXVIII). Methyl-3,5,6-trifluorobenzyl(1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compounds of the invention) 49) 17mg:

[化68]。[化68] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例20：本發明化合物55的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(49mg、0.26mmol)及4-二甲胺基吡啶(3mg)加到2-溴-4-甲氧基甲基-3,5,6-三氟苯甲醇(48mg、0.17mmol)及(1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷甲酸(53mg、0.25mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌20小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化69](XXIX)表示的2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(2,2-二氯-1-乙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物55)66mg：Production Example 20: Production of Compound 55 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (49 mg, 0.26 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (48 mg, 0.17 mmol) and (1R)-trans-3-(2,2-dichloro- 1-vinyl)-2,2-dimethylcyclopropanecarboxylic acid (53 mg, 0.25 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. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-4-methoxy group represented by the following formula [69] (XXIX). Methyl-3,5,6-trifluorobenzyl (1R)-trans-3-(2,2-dichloro-1-vinyl)-2,2-dimethylcyclopropanecarboxylate (this Inventive compound 55) 66 mg:

[化69]。[化69] .

無色液體：1 H-NMR(CDCl3 ，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)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)

製造例21：本發明化合物62的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(38mg、0.20mmol)及4-二甲胺基吡啶(3mg)加到2-溴-4-甲氧基甲基-3,5,6-三氟苯甲醇(36mg、0.13mmol)及(1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷甲酸(關於雙鍵的異構物的比率：Z/E=約8/1)(30mg、0.20mmol)的三氯甲烷溶液(3mL)。在室溫下攪拌18小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化70](XXX)表示的2-溴-4-甲氧基甲基-3,5,6-三氟苄基 (1R)-反式-3-(1-丙烯基)-2,2-二甲基環丙烷羧酸酯(本發明化合物62)(關於雙鍵的異構物的比率：Z/E=約8/1)22mg：Production Example 21: Production of Compound 62 of the Present Invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (38 mg, 0.20 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (36 mg, 0.13 mmol) and (1R)-trans-3-(1-propenyl)-2 , a solution of 2-dimethylcyclopropanecarboxylic acid (ratio of the isomer of the double bond: Z/E = about 8/1) (30 mg, 0.20 mmol) in chloroform (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-4-methoxy group represented by the following formula [Chem. 70] (XXX). Methyl-3,5,6-trifluorobenzyl(1R)-trans-3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Compound 62 of the invention) The ratio of isomers of the bond: Z/E = about 8/1) 22 mg:

[化70]。[化70] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.12(s，3H，Z+E體)、1.26(s，3H，Z+E體)、1.46(d，1H，Z+E體)、1.71(dd，3H，Z+E體)、2.18(m，1H，Z+E體)、3.40(s，3H，Z+E體)、4.58(m，2H，Z+E體)、5.11(m，1H，Z+E體)、5.30(m，2H，Z+E體)、5.61(m，1H，Z+E體)Colorless liquid: 1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.12 (s, 3H, Z+E), 1.26 (s, 3H, Z+E), 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)

製造例22：本發明化合物69的製造 將1-乙基-3-(3-二甲胺基丙基)碳二亞胺鹽酸鹽(30mg、0.16mmol)及4-二甲胺基吡啶(3mg)加到2-溴-4-甲氧基甲基-3,5,6-三氟苯甲醇(30mg、0.11mmol)及2,2,3,3-四甲基環丙烷甲酸(23mg、0.16mmol)的三氯甲烷溶液(2mL)。在室溫下攪拌24小時後，將水注加到反應液，以乙酸乙酯萃取反應液。以硫酸鎂將該有機層乾燥後，在減壓條件下濃縮，將殘渣附加於矽膠管柱層析，得到以下列的式[化71](XXXI)表示的2-溴-4-甲氧基甲基-3,5,6-三氟苄基 2,2,3,3-四甲基環丙烷羧酸酯(本發明化合物69)18mg：Production Example 22: Production of Compound 69 of the present invention 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (30 mg, 0.16 mmol) and 4-dimethylaminopyridine ( 3 mg) was added to 2-bromo-4-methoxymethyl-3,5,6-trifluorobenzyl alcohol (30 mg, 0.11 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (23 mg, 0.16 mmol) of chloroform solution (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. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was applied to a silica gel column chromatography to give 2-bromo-4-methoxy group represented by the following formula [71] (XXXI). Methyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (Compound 69 of the invention) 18 mg:

[化71]。[71] .

無色液體：1 H-NMR(CDCl3 ，TMS)δ(ppm)：1.17(s，7H)、1.25(s，6H)、3.40(s，3H)、4.59(m，2H)、5.30(m，2H)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)

其次，顯示製劑例。此外，份是表示質量份。Next, a formulation example is shown. In addition, the serving is a part by mass.

製劑例1 將本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各0.1份溶解於二甲苯10份，將其混合於脫臭煤油89.9份，得到油劑。Formulation Example 1 0.1 parts of each of the compounds of the present invention, 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69, was dissolved in 10 parts of xylene, and mixed with 89.9 parts of deodorized kerosene. , get oil.

製劑例2 將混合溶解了本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各0.1份及脫臭煤油39.9份之物填充於噴霧罐容器，安裝了閥部分後，經由該閥部分加壓填充噴射劑(液化石油氣)60份，得到油性噴霧罐。Formulation Example 2 0.1 part of each of the compounds 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 of the present invention and 39.9 parts of deodorized kerosene were mixed and filled in a spray can container. After the valve portion was attached, 60 parts of the propellant (liquefied petroleum gas) was pressurized and filled through the valve portion to obtain an oily spray can.

製劑例3 將混合溶解了本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各0.6份、二甲苯5份、脫臭煤油3.4份及RHEODOL MO-60(乳化劑，花王股份有限公司註冊商標)1份之物，與水50份填充於噴霧罐容器，經由閥部分加壓填充噴射劑(液化石油氣)40份，得到水性噴霧罐。Formulation Example 3 0.6 parts of each of the compounds of the present invention, 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69, 5 parts of xylene, 3.4 parts of deodorized kerosene, and RHEODOL were dissolved. One part of MO-60 (emulsifier, registered trademark of Kao Co., Ltd.) was filled in a spray can container with 50 parts of water, and 40 parts of a propellant (liquefied petroleum gas) was pressurized and filled through a valve portion to obtain an aqueous spray can.

製劑例4 將本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各0.3g及BHT0.5g均勻攪拌混合於蚊香用基材(混合了除蟲菊萃取糟粉、木粉、紅楠粉及澱粉之物)99.2g後，將加入包含作為著色劑的孔雀綠的水100mL，充分混練後之物成型乾燥，得到蚊香。Formulation Example 4 0.3 g of each of the compounds of the present invention, 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 and 0.5 g of BHT were uniformly stirred and mixed on a substrate for mosquito coils (mixed except After 99.2 g of the extract of Cordyceps extract, wood powder, red lotus powder and starch, 100 mL of water containing malachite green as a coloring agent was added, and the mixture was thoroughly kneaded and dried to obtain mosquito coils.

製劑例5 將脫臭煤油加到本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各0.8g、胡椒基丁醚0.4g及染料並溶解，全部以10mL。將該溶液0.5mL均勻含浸於22mm×35mm、厚度2.8mm的蚊香片用基材(將棉籽絨與紙漿的混合物的原纖維凝固成板狀者)，得到蚊香片劑。Formulation Example 5 Deodorized kerosene was added to each of the compounds of the present invention, 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69, 0.8 g each, and piperonyl butoxide (0.4 g) and a dye was dissolved. , all in 10mL. 0.5 mL of this solution was uniformly impregnated into a substrate for a mosquito-repellent sheet of 22 mm × 35 mm and a thickness of 2.8 mm (the fibrils of a mixture of cotton linter and pulp were solidified into a plate shape) to obtain a mosquito-repellent tablet.

製劑例6 將本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各0.7份及BHT0.3份溶解於界面活性劑(二乙二醇單丁醚)50份與淨化水49份而得的液劑放入聚酯製容器，藉由***能以加熱器將上部加熱的吸液芯(將無機粉體燒成者)，得到加熱蒸散裝置所使用的水性蚊香液劑。Formulation 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 parts of BHT were dissolved in a surfactant (diethylene glycol alone) 50 parts of butyl ether and 49 parts of purified water are placed in a polyester container, and a wick (heating the inorganic powder) capable of heating the upper portion by a heater is inserted to obtain a heating evapotranspiration device. The aqueous mosquito liquid used.

製劑例7 將本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各3.0份、惡蟲酮3.0份及偶氮二甲醯胺94.0份充分混合後，將其20g填充到塑膠膜袋，將其收納於耐熱容器並裝填點火器得到燻煙劑。Formulation Example 7 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 oxafluridone and 94.0 parts of azomethoxamine were sufficiently After mixing, 20 g of the film was filled in a plastic film bag, and it was housed in a heat-resistant container and filled with an igniter to obtain a fumigation agent.

製劑例8 將本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各10mg溶解於適量的丙酮，均勻塗佈於5cm×5cm、厚度0.3mm的不織布後，將丙酮風乾，得到常溫揮散劑。Formulation Example 8 10 mg of each of the compounds of the present invention, 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69, was dissolved in an appropriate amount of acetone, and uniformly applied to a thickness of 5 cm × 5 cm and a thickness of 0.3 mm. After the non-woven fabric, the acetone was air-dried to obtain a normal temperature dispersing agent.

製劑例9 將本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的各10份、包含聚氧乙烯烷基醚硫酸銨鹽50份的白碳35份及水55份混合，藉由以濕式粉碎法進行微粉碎，得到10%流動劑。Formulation Example 9 10 parts of each of the compounds of the present invention, 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69, and 50 parts of white carbon containing ammonium polyoxyethylene alkyl ether sulfate 35 parts and 55 parts of water were mixed and finely pulverized by a wet pulverization method to obtain a 10% flow agent.

其次，顯示以本發明化合物作為有害生物防除劑的有效成分有效當作試驗例。Next, it is shown that the active ingredient of the compound of the present invention as a pest control agent is effectively used as a test example.

效果試驗例1(使用淡色庫蚊的接觸試驗) 將包含0.1mg的本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的0.2%丙酮溶液0.05mL滴下到直徑28mm、內高13mm、底面積6.15cm2 之培養皿，均勻地擴展於底面後，以二連球去除丙酮。將淡色庫蚊的雌6隻放入各試樣被保持於底面的培養皿，以開孔的膜覆蓋上側後，每1分記錄擊倒數，測定且記錄了KT50 (50%擊倒的時間)與24小時後的致死率。關於就擊倒率顯示規定以上的數值的試樣係更將丙酮加到前述0.2%丙酮溶液稀釋成10倍，當作0.02%丙酮溶液，依次重複了前述的各器具(培養皿)、試驗方法。 而且，作為比較對照使用胺菊酯：1,3,4,5,6,7-六氫-1,3-二氧代-2H-異吲哚-2-基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(以下記為比較化合物A)，同樣地進行了試驗。 將結果顯示於表4Effect Test Example 1 (contact test using Culex pipiens pallens) 0.2% acetone solution containing 0.1 mg of the compounds of the present invention 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 The mL was dropped into a petri dish having a diameter of 28 mm, an inner height of 13 mm, and a bottom area of 6.15 cm 2 , and uniformly spread to the bottom surface, and the acetone was removed by two balls. Six females of Culex pipiens pallens were placed in a petri dish with each sample held on the bottom surface, and the upper side was covered with an open-cell membrane. The number of knockdowns was recorded every 1 minute, and KT 50 was measured and recorded (50% knockdown Time) and lethality after 24 hours. Regarding the sample in which the above-mentioned numerical value is specified as the knockdown rate, the acetone is added to the above-mentioned 0.2% acetone solution and diluted to 10 times, and the above-mentioned respective instruments (culture dishes) and test methods are sequentially repeated as a 0.02% acetone solution. . Moreover, as a comparative control, the use of methrin: 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-dimethylcyclopropanecarboxylate (hereinafter referred to as Comparative Compound A) was tested in the same manner. The results are shown in Table 4.

【表4】 【Table 4】

試驗的結果得知本發明化合物3，9，16，23，26，32，39，46，49，55，62及69都顯示超過比較化合物A(胺菊酯)之高的擊倒率。As a result of the test, it was found that the compounds of the present invention 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69 all showed a higher knockdown rate than the comparative compound A (methrin).

效果試驗例2(使用淡色庫蚊的常溫揮散性試驗) 將淡色庫蚊的雌10隻放入直徑9cm、內高1.9cm、底面積63.6cm2 之培養皿，以16網目的金屬絲網覆蓋。將包含0.09mg的所調製的藥劑的本發明化合物23，46及69的2%丙酮溶液0.5mL滴下到相同尺寸的培養皿(直徑9cm、內高1.9cm、底面積63.6cm2 )，將丙酮風乾。接著，將塗佈了該藥劑的培養皿倒置於上述金屬絲網之上。然後每1分調查擊倒的淡色庫蚊的雌成蟲的數，求擊倒率。 而且，作為比較對照使用益避寧：(RS)-(EZ)-1-乙炔基-2-甲基-2-戊烯基 (1R)-反式,順式-3-(2-甲基-1-丙烯基)-2,2-二甲基環丙烷羧酸酯(以下記為比較化合物B)，同樣地進行了試驗。 將結果顯示於表5Effect test example 2 (normal temperature volatilization test using Culex pipiens pallens) 10 females of Culex pipiens pallens were placed in a petri dish having a diameter of 9 cm, an inner height of 1.9 cm, and a bottom area of 63.6 cm 2 , and covered with a wire mesh of 16 mesh. . 0.5 mL of a 2% acetone solution of the present compounds 23, 46 and 69 containing 0.09 mg of the prepared medicament was dropped into a Petri dish of the same size (diameter 9 cm, inner height 1.9 cm, bottom area 63.6 cm 2 ), acetone Air dried. Next, the petri dish coated with the drug was poured on the above-mentioned wire mesh. Then, the number of female adults of Culex pipiens pallens was knocked down every 1 minute to find the knockdown rate. Moreover, as a comparative control, Yixu Ning was used: (RS)-(EZ)-1-ethynyl-2-methyl-2-pentenyl (1R)-trans, cis-3-(2-methyl 1-propenyl)-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as Comparative Compound B) was tested in the same manner. The results are shown in Table 5.

【表5】 【table 5】

試驗的結果得知本發明化合物23，46及69都顯示超過比較化合物B(益避寧)之高的擊倒率。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 the comparative compound B (Yi Ning).

效果試驗例3(利用蚊香進行的殺蟲試驗) 將淡色庫蚊成蟲約50隻釋放到70cm立方的玻璃箱內，將電池式小型風扇(葉片的直徑13cm)設置於箱內使其旋轉。一將藉由製劑例4得到的本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的蚊香0.1g的兩端點火後放入玻璃箱，在15分以內就能使80%以上的淡色庫蚊擊倒，在翌日就能使其80%以上致死。Effect Test Example 3 (Insecticide Test by Mosquito Repellent) About 50 adult Culex pipiens pallens were released into a 70 cm cubic glass box, and a battery type small fan (leaf diameter of 13 cm) was placed in the box to be rotated. One of the compounds of the present invention obtained by Formulation Example 4, 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69, was ignited at 0.1 g in both ends and placed in a glass box. Within 15 minutes, more than 80% of Culex pipiens pallens can be knocked down, and more than 80% of them can be killed in the next day.

效果試驗例4(利用燻煙劑進行的殺蟲試驗) 在6榻榻米的房間使用加熱器將比照製劑例7調製的本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的燻煙劑1袋加熱到約250℃的結果，成分由以塑膠膜形成的噴煙孔擴散到房間全體，對以蟑螂、蚤、臭蟲為首，以及室塵蟎或腐食酪蟎等的家塵蟎類的防除也有效。Effect Test Example 4 (Insecticidal test by fumigation agent) The compound of the present invention prepared in accordance with Formulation Example 7 was used in a room of 6 tatami, 3, 9, 16, 23, 26, 32, 39, 46, 49. The bag of the fumigation agent of 55, 62, and 69 is heated to about 250 ° C. As a result, the composition is diffused to the entire room by a puff hole formed of a plastic film, and is led by cockroaches, cockroaches, bed bugs, and dust mites or rot. The control of house dust mites such as cockroaches is also effective.

效果試驗例5(利用噴霧罐進行的殺蟲試驗) 將家蠅雌成蟲約30隻釋放到60cm立方的玻璃箱內，由箱子的側壁的孔每一秒鐘將藉由製劑例2得到的本發明化合物3，9，16，23，26，32，39，46，49，55，62及69的噴霧罐噴霧。其結果，在2分以內能使100%的家蠅擊倒，認定了本發明化合物具有高的擊倒效果。Effect Test Example 5 (Insecticide Test by Spray Can) About 30 female adult females of Musca domestica were released into a 60 cm cubic glass box, and the hole obtained from the side wall of the box was obtained by Formulation Example 2 per second. Spray can sprays of the inventive compounds 3, 9, 16, 23, 26, 32, 39, 46, 49, 55, 62 and 69. As a result, 100% of the housefly was knocked down within 2 minutes, and it was confirmed that the compound of the present invention has a high knocking effect.

本發明化合物因具有優良的有害生物防除效力，故可當作有害生物防除劑的有效成分利用。而且，本發明化合物具有也能當作對獲得了抵抗性的有害生物的防除劑的有效成分利用的可能性，極為有效。Since the compound of the present invention has excellent pest control effect, it can be utilized as an active ingredient of a pest control agent. Further, the compound of the present invention is extremely effective in that it can be used as an active ingredient of a controlling agent for a pest that has obtained resistance.

Claims (8)

一種酯化合物，以下列的通式[化1](1)表示： [化1][式中R1 是表示氫原子或甲基，R1 表示甲基時R2 也表示甲基，而且R1 表示氫原子時R2 為以下列通式[化2](2) [化2](此處X及Y為同一或不同，表示氫原子、鹵素原子、氰基、碳數1~4的烷基、碳數2~5的烷氧基羰基或碳數1~4的鹵烷基)表示的基，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]。An ester compound represented by the following formula [Chemical Formula 1] (1): [Chemical Formula 1] Wherein R 1 represents a hydrogen atom or a methyl group, R 1 represents a methyl group, and R 2 also represents a methyl group, and when R 1 represents a hydrogen atom, R 2 is in the following formula [Chemical 2] (2) [Chemical 2 ] (wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms. Wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propynyl group. 一種酯化合物，以下列的通式[化3](I)表示： [化3][式中R1 是表示氫原子或甲基，R1 表示甲基時R2 也表示甲基，而且R1 表示氫原子時R2 為以下列通式[化4](II) [化4](此處X及Y為同一或不同，表示氫原子、鹵素原子、氰基、碳數1~4的烷基、碳數2~5的烷氧基羰基或碳數1~5的鹵烷基)表示的基，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]。An ester compound represented by the following formula [Chemical Formula 3] (I): [Chemical 3] Wherein R 1 represents a hydrogen atom or a methyl group, R 1 represents a methyl group, and R 2 also represents a methyl group, and when R 1 represents a hydrogen atom, R 2 is represented by the following formula [Chemical Formula 4] (II) [Chemical 4 ] (wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. Wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propynyl group. 如申請專利範圍第1項或第2項之酯化合物，其中R3 是以氫原子表示。An ester compound according to claim 1 or 2, wherein R 3 is represented by a hydrogen atom. 如申請專利範圍第1項或第2項之酯化合物，其中R3 是以甲基表示。An ester compound according to claim 1 or 2, wherein R 3 is represented by a methyl group. 如申請專利範圍第1項或第2項之酯化合物，其中R3 是以甲氧基甲基表示。An ester compound according to claim 1 or 2, wherein R 3 is represented by a methoxymethyl group. 如申請專利範圍第1項或第2項之酯化合物，其中R3 是以乙炔基表示。An ester compound according to claim 1 or 2, wherein R 3 is represented by an ethynyl group. 一種有害生物防除劑，含有以申請專利範圍第1項至第6項中任一項的酯化合物作為有效成分。A pest control agent containing the ester compound according to any one of claims 1 to 6 as an active ingredient. 一種有害生物的防除方法，將申請專利範圍第1項至第6項中任一項的酯化合物施用於有害生物或有害生物的棲息地。A method for controlling pests, which comprises applying the ester compound according to any one of claims 1 to 6 to a habitat of a pest or a pest.
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