TW200932723A - Cyclopropanecarboxylate and use thereof - Google Patents

Cyclopropanecarboxylate and use thereof Download PDF

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TW200932723A
TW200932723A TW097143796A TW97143796A TW200932723A TW 200932723 A TW200932723 A TW 200932723A TW 097143796 A TW097143796 A TW 097143796A TW 97143796 A TW97143796 A TW 97143796A TW 200932723 A TW200932723 A TW 200932723A
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group
compound
formula
acid
reaction
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TW097143796A
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Noritada Matsuo
Masayuki Mae
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Sumitomo Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C255/48—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of 2,2-dimethylcyclopropane rings, e.g. nitrile of chrysanthemumic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

There is provided a novel cyclopropanecarboxyate of the formula (1): wherein R1 represents a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, a (C1-C4 alkyl)oxymethyl group or a (C1-C4 alkyl)thiomethyl group. The cyclopropanecarboxyate has excellent pest control effect.

Description

200932723 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種環丙烷羧酸酯及其用途。 【先前技術】 迄今，已合成許多化合物以用於防治害蟲。例如，JP 53-108951A揭露某些種類的環丙烷羧酸酯衍生物。但是， 上揭文獻中所述之環丙烷羧酸醋衍生物的害蟲防治效果仍 不夠尚。 ❹【發明内容】 本發明之目的係提供一種具有優異的害蟲防治效果之 新穎化合物。 本案發明人已進行深入的研究且發現後文所示的式（I) 之酯化合物具有優異的害蟲防治效果。因而完成本發明。 亦即，本發明提供： [1] 一種式（1)之環丙烷羧酸酯（後文中有時稱為本發明化200932723 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a cyclopropanecarboxylate and its use. [Prior Art] To date, many compounds have been synthesized for controlling pests. For example, JP 53-108951 A discloses certain types of cyclopropanecarboxylate derivatives. However, the pest control effect of the cyclopropanecarboxylic acid vinegar derivative described in the above publication is still insufficient. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound having excellent pest control effects. The inventors of the present invention have conducted intensive studies and found that the ester compound of the formula (I) shown later has an excellent pest control effect. Thus the present invention has been completed. That is, the present invention provides: [1] A cyclopropanecarboxylate of the formula (1) (hereinafter sometimes referred to as the present invention)

式中，R1表示氫原子、氟原子、C1-C4烷基、C2-C4烯基、 C2-C4炔基、C1-C4烷氧基、（C1-C4烷基）氧基曱基或（Cl-C4 烷基）硫甲基； [2]根據第[1]項之環丙烷羧酸酯，其中，R1為氫原子、氟 原子、甲基、2-丙烯基、2-丙炔基、甲氧基、甲氧基甲基 或曱基硫曱基； 3 320738 200932723 [3]、種害蟲防治組成物，包括第[1]或[2]項之環丙烷羧酸 酯作為活性成分； =]種害蟲防治方法，包括對害蟲或害蟲棲息地施用有效 里之第[1]或[2]項之環丙烷羧酸酯；及 種用於製造第[丨]或[2]項之環丙烷羧酸酯之方法，其 包括下歹步驟： 在猛^^了之氧化物的存在中，使式⑻之化合物： ❹In the formula, R1 represents a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, a (C1-C4 alkyl)oxyfluorenyl group or (Cl). [C4 alkyl] thiomethyl; [2] The cyclopropanecarboxylate according to [1], wherein R1 is a hydrogen atom, a fluorine atom, a methyl group, a 2-propenyl group, a 2-propynyl group, Oxy, methoxymethyl or decylthiol group; 3 320738 200932723 [3], a pest control composition comprising the cyclopropanecarboxylate of item [1] or [2] as an active ingredient; Method for controlling pests, comprising applying a cyclopropanecarboxylate of item [1] or [2] in an effective pest or pest habitat; and producing a cyclopropanecarboxylate of the item [丨] or [2] A method of an acid ester comprising the step of: hydrating a compound of formula (8) in the presence of an oxide of lanthanum: ❹

CN (6) 酸鹽反應而獲得式（3)之CN (6) acid salt reaction to obtain formula (3)

HOHO

CN 羧酸 (3) 而獲得該環丙烷羧酸 ::及使式⑻之巍與式⑵之醇反應 ΟCN carboxylic acid (3) to obtain the cyclopropanecarboxylic acid :: and react the oxime of formula (8) with the alcohol of formula (2) Ο

(2) ^中CM W表示氫原子、氟原子、C1_C4烧基、C2-C4烯基 烷基基crc4燒氧基、（C1-C4烧基)氧基甲基或（ci- 化人^本㈣化合物財優㈣#蟲_效果，因此 為害蟲防治組成物之活性^ 本發明化合物中，在環丙烧環上的卜及3-位置處有 320738 200932723 個不對稱碳。環丙烷環之c〗碳原子的絕對組態（absolute configuration)為R-組態，而環丙烷環之C3碳原子則為 S-組態。C1和C3碳原子的相對立體化學為順式（cis)。亦 即，本發明化合物為（1R)-順式-環呙烷羧酸酯。 本發明中， C1-C4烷基之實例包含甲基、乙基及丙基； C2-C4烯基之實例包含乙烯基及2-丙烯基； > C2-C4炔基之實例包含乙炔基及2-丙炔基； C1-C4烷氧基之實例包含甲氧基、乙氧基及丙氧基； (a-c4絲）氧基甲基之實例包含甲氧基甲基、 基及丙氧基甲基;及 ^ γ (C1-C4烷基）硫甲基之實例包含曱基硫甲基、 及丙基硫曱基。(2) ^ CM W represents a hydrogen atom, a fluorine atom, a C1_C4 alkyl group, a C2-C4 alkenylalkyl group crc4 alkoxy group, a (C1-C4 alkyl)oxymethyl group or (ci-chemical group) (4) Compound Caiyou (4) #虫_effect, therefore the activity of the pest control composition ^ In the compound of the present invention, there are 320738 200932723 asymmetric carbons on the propylene ring and the 3-position. The cyclopropane ring c The absolute configuration of the carbon atom is the R-configuration, while the C3 carbon atom of the cyclopropane ring is the S-configuration. The relative stereochemistry of the C1 and C3 carbon atoms is cis. The compound of the present invention is (1R)-cis-cyclodecanecarboxylate. In the present invention, examples of the C1-C4 alkyl group include a methyl group, an ethyl group and a propyl group; and examples of the C2-C4 alkenyl group include a vinyl group. And 2-propenyl; > Examples of C2-C4 alkynyl group include ethynyl group and 2-propynyl group; examples of C1-C4 alkoxy group include methoxy group, ethoxy group and propoxy group; (a-c4 Examples of the silk)oxymethyl group include a methoxymethyl group, a group and a propoxymethyl group; and examples of the γ (C1-C4 alkyl) thiomethyl group include a mercaptothiomethyl group, and a propyl sulfonium group. base.

其中R1件如上文所述者， 乙基硫甲基 及式（3)之羧酸：Wherein R1 is as described above, ethylthiomethyl and the carboxylic acid of formula (3):

。用於此反應之 1定、二乙基 3207^ 5 200932723 苯胺、4-二曱基胺基吡啶及二異丙基乙胺。用於此反應之 溶劑包含於反應中呈惰性之彼等溶劑。該等溶劑之具體只 例包含烴類，例如曱苯及己烷；醚類，例如二乙醚及四氫 呋喃；鹵化烴類，例如氣仿、二氯曱烷及L 2一二氯乙炫* ’ 及其混合溶劑。 反應性衍生物之實例包含羧酸之醯基齒化物、叛酸之 酸酐及羧酸之低級烷基酯。 此反應之反應時間通常從瞬時至72小時，而反應溫度 通常在-20°C至100°C之範圍内。 相對於每莫耳（mol)羧酸或其反應性衍生物’用於反應 之醇化合物理論上係以1莫耳的量使用，較適當者’相對 於每莫耳該竣酸或其反應性衍生物，係以0· 5至1. 5莫耳 的量使用。相對於每莫耳該羧酸或其反應性衍生物’用於 此反應之鹼的量通常為1莫耳，但該用量可根據反應條件 適當地選擇。 ❹ 此反應完成後，本發明化合物可經單離，例如，可藉 由使反應混合物進㈣知操作（例如將反應混合物倒入^ 中，接著以有機溶劑萃取及進一步濃縮）而予以單離右 需要’經此方式單離之本發明化合物可獅層析法及蒸^ 式⑵之醇化合物係詳述於Jp MU 了 7 123146Α ' JP 61-207361A » ττ, , , ~ 及JP 11 -222463中，且可粝媸 此等文獻所述之方法來製備。 彳根艨 式（3)之羧酸可藉由例如 ’後文所述步驟1 之方法來製 320738 6 200932723 備0 竣酸之反應性衍生物可藉由已知 雜 酸作為起始材料來製備。，使用式⑶之竣 較佳者，本發明化合物 該方法包括下財驟： ㈣地製備’ 合物 在錄，舒之氧化物存在下，使式(6)之化 ❹. Used in this reaction, di-, diethyl 3207^ 5 200932723 aniline, 4-didecylaminopyridine and diisopropylethylamine. The solvent used in this reaction contains the solvents which are inert in the reaction. Specific examples of such solvents include hydrocarbons such as toluene and hexane; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as gas, methylene chloride and L 2 -dichloroethane*' and Its mixed solvent. Examples of the reactive derivative include a mercaptodentate of a carboxylic acid, an acid anhydride of a carboxylic acid, and a lower alkyl ester of a carboxylic acid. The reaction time for this reaction is usually from the instant to 72 hours, and the reaction temperature is usually in the range of from -20 ° C to 100 ° C. The alcohol compound used for the reaction is theoretically used in an amount of 1 mole relative to each mole (mol) of the carboxylic acid or its reactive derivative, and the appropriate one is relative to the citric acid per mole or its reactivity. The derivative is used in an amount of from 0.5 to 1.5 moles. The amount of the base used in the reaction with respect to the carboxylic acid or its reactive derivative per mole is usually 1 mole, but the amount may be appropriately selected depending on the reaction conditions. ❹ After completion of the reaction, the compound of the present invention may be isolated, for example, by subjecting the reaction mixture to a known operation (for example, pouring the reaction mixture into a solvent, followed by extraction with an organic solvent and further concentration). It is required that the compound of the present invention which is isolated in this manner can be lanced and vaporized. The alcohol compound of the formula (2) is described in detail in Jp MU 7 123146 Α ' JP 61-207361A » ττ, , , ~ and JP 11 -222463 And can be prepared by the methods described in these documents. The carboxylic acid of the formula (3) can be produced by, for example, the method of the step 1 described later. 320738 6 200932723 The reactive derivative of decanoic acid can be prepared by using a known hetero acid as a starting material. . Preferably, the compound of the present invention comprises the following formula: (4) Preparation of a compound </ br>

/ CN :合:=):::)舆式⑵之酵一本發 溶劑m在溶繼下進行。用於此反應. 」丁:==劑之實例包含醇類溶劑，例如 如乙腈及丙腈；及酿胺溶劑，例如甲^乙基嗣；腈溶劑，‘ 甲基轉唆酮。 例如N，N〜二甲基甲酿胺及丨 實例包含偏過碟酸納及偏過蛾酸鉀。 化物鈉及過_， 或句之氧化物可得以在步驟/以錄釕⑽水合物。 相對於每莫耳式⑻之化^相同反應介質中製備 氣化物的量通常為（U^f此反應德或句 之作人異耳，而相對於每莫耳式ri 化合物，過碟酸鹽的量通常為2至30莫耳。 ° 200932723 此反應之反應時間通常為12至9 6小時之間，而.反應 溫度通常為0至50°C。 反應完成後，式（3 )之化合物可經單離，例如，可藉由 使反應混合物進行習知操作（例如將反應混合物倒入水 中，接著以有機溶劑萃取及進一步濃縮）而予以單離。 步驟2之反應通常在溶劑内於酸催化劑或縮合劑存在 下進行。用於此反應之溶劑包含於反應中呈惰性之彼等溶 .劑。該等溶劑之具體實例包含烴類，例如曱苯及己烷；醚 類，例如二乙醚及四氫呋喃；函化烴類，例如氯仿、二氯 甲烷及1，2-二氯乙烷；及其等之混合溶劑。 酸催化劑之實例包含無機酸類，例如硫酸；及磺酸類， 例如對曱苯磺酸及甲磺酸。相對於每莫耳該羧酸，用於此 反應之酸催化劑的量通常在0·01至2〇莫耳之範圍内，但 該用量可根據反應條件適當地選擇。 此反應中之縮合劑之實例包含二環己基碳二亞胺及卜 ❹乙基_3~(3-二曱基胺基丙基）碳二亞胺鹽酸鹽。相對於每莫 耳該羧酸，用於此反應之縮合劑的量通常為丨莫耳，但該 用量可根據反應條件適當地選擇。 步驟2中，反應時間通常為瞬時至72小時之間，而反 應溫度通常在-20°C至l〇〇°c之範圍内。 反應元成後’本發明化合物可經單離，例如，可藉由 使反應混合物進行習知操作（例如將反應混合物倒入水 中，接著以有機溶劑萃取及進一步濃縮）而予以單離。若有 需要’經此方式單離之本發明化合物係藉由層析法及蒸餾 8 320738 200932723 而純化〇 . 式（6)之化合物係例如’根據JP5_246971 Α或J. 〇rg. Chem· 2003’ 68’ 621-624所述之方法而製備，或藉由下 述流程圖所示之方法而製備。/ CN :合:=):::)) The leave of the formula (2) The solvent m is carried out under the conditions of dissolution. For the reaction. "Examples of the din:== agent include alcohol solvents such as acetonitrile and propionitrile; and amine solvent such as methyl ethyl hydrazine; nitrile solvent, 'methyl fluorenone. For example, N,N~dimethylamylamine and hydrazine examples include sodium sulphate and potassium molybdate. The sodium compound and the oxide of the _, or sentence can be obtained in the step / to record the hydrazine (10) hydrate. The amount of gas formed in the same reaction medium per mole of (8) is usually (U^f this reaction or sentence is made into a human ear, and relative to each mole of ri compound, over-dissolved salt) The amount is usually from 2 to 30 mol. ° 200932723 The reaction time of this reaction is usually between 12 and 96 hours, and the reaction temperature is usually from 0 to 50 ° C. After the reaction is completed, the compound of formula (3) can be used. Isolation can be carried out, for example, by subjecting the reaction mixture to a conventional operation (for example, pouring the reaction mixture into water, followed by extraction with an organic solvent and further concentration). The reaction of step 2 is usually carried out in a solvent over an acid catalyst. Or the solvent is used in the presence of a condensing agent. The solvent used in the reaction comprises the same solvent which is inert in the reaction. Specific examples of the solvent include hydrocarbons such as toluene and hexane; ethers such as diethyl ether and Tetrahydrofuran; a functionalized hydrocarbon such as chloroform, dichloromethane, and 1,2-dichloroethane; and a mixed solvent thereof, etc. Examples of the acid catalyst include inorganic acids such as sulfuric acid; and sulfonic acids such as p-sulfonate Acid and methanesulfonic acid. The amount of the acid catalyst used in the reaction is usually in the range of from 0.001 to 2 Torr per mole of the carboxylic acid, but the amount may be appropriately selected depending on the reaction conditions. Examples of the condensing agent in the reaction Containing dicyclohexylcarbodiimide and dipyridylethyl-3-(3-didecylaminopropyl)carbodiimide hydrochloride. Condensation for this reaction relative to the carboxylic acid per mole The amount of the agent is usually 丨mol, but the amount can be appropriately selected according to the reaction conditions. In the step 2, the reaction time is usually from instantaneous to 72 hours, and the reaction temperature is usually from -20 ° C to 10 ° C. Within the scope of the reaction, the compound of the present invention can be isolated, for example, by subjecting the reaction mixture to a conventional operation (for example, pouring the reaction mixture into water, followed by extraction with an organic solvent and further concentration). If necessary, the compound of the present invention which is isolated in this manner is purified by chromatography and distillation 8 320738 200932723. The compound of the formula (6) is, for example, 'according to JP5_246971 Α or J. 〇rg. Chem· Prepared by the method described in 2003' 68' 621-624 Or prepared by the method shown in the following flow chart.

Λ反應係藉线式⑷之化合物㈣化劑（例如草酿氯) 反應’接者與氨反應而進行。 就舰常在㈣崎行。祕此反應之溶劑之實例 包含醚溶劑，例如四氫D夫喃。 相對於每莫耳式⑷之化合物，用於此反應之氯化劑的 用量理論上為1莫耳，值可適當地在i莫耳至過量，且較 佳在1莫耳至3莫耳的範圍内選擇。若有需要，式⑷之化 ❹合物可與氯化劑在鹼存在下反應。驗之實例包含三乙胺及 吼咬。式（4)之化合物與氯化劑之反應通常進行丨至24小 時。反應温度通常為〇。(^至5〇 °c。 與氨之反應通常係藉由將氨氣或氨水注入到上述步驟 之反應混合物或其濃縮物中而進行。 相對於每莫耳式（4)之化合物，氨的用量理論上為丨莫 耳，但可適當地在1莫耳至過量，且較佳在1莫耳至3莫 耳的範圍内選擇。進行與氨之反應的反應時間通常為1至 24小時’而反應溫度通常為〇〇c至5(TC。 〇 320738 200932723 反應完成後，式（5)之化合物可經單離，例如，可藉由 使反應混合物進行習知操作（例如將反應混合物倒入水 中，接著以有機溶劑萃取及進一步濃縮）而予以單離。 從式（5)之犯合物至式（6)之化合物之反應 此反應係藉由使式（5)之化合物與醋酸酐反應而進行。 相對於每1莫耳式（5)之化合物，此反應中之醋酸酐的 用量在5莫耳至過量的範圍内。 '. 此反應之反應時間通常在1至24小時範圍内，而反應 ❹ 溫度通常在25°C至醋酸酐的回流溫度之範圍内。 反應完成後’式（6 )之化合物可經單離，例如，可藉由 使反應混合物進行習知操作（例如將反應混合物倒入水 中，接著以有機溶劑萃取及進一步濃縮）而予以單離。若有 需要，經此方式獲得之經單離的式（6)之化合物係藉由層析 法而純化。 式（4)之化合物可例如，藉由根據jp 2001-278851 A 〇 所述方法適當地純化所製得之菊酸（chrysanthemic aCid) 而製備，或可藉由根據jP U-279111 A所述光學離析法之 純化方法所製得之濾液而獲得。 本發明化合物對其見效之害蟲之實例包含有害節肢動 物’例如有害昆蟲及有害蟲蝨。該等有害節肢動物之具體 實例如下列者。 鱗翅目（Le^idoptera): 螟蛾科（Pyralidae)，例如二化螟蛾（Chilo uppressalis)、稻縱捲葉野埃蛾（cnaphai〇cr〇cis 10 320738 200932723 1^(1111&amp;113)及印度穀粉模蛾（？1〇(^3 111士6印11110^6113);夜 蛾科（Noctuidae) ’ 例如斜紋夜蛾（spodoptera litura)、 東方黏蟲（Pseudaletia separata)及甘藍夜蛾（Mamestra brassicae);粉蝶科（Pieridae)，例如紋白蝶（Pieris rapaecrucivora);捲蛾科（Tortricidae)，例如小捲葉蛾 屬（Adoxophyes spp.);果蛀蛾科（Carposinidae);潛蛾科 (Lyonetiidae);毒蛾科（Lymantriidae);銀紋夜蛾 (Autographa);夜蛾屬（Agrothis spp.)，例如蕪菁夜蛾 〇 (Agrotis segetum)及球菜夜蛾（Agrotis ipsilon);實夜 蛾屬（Helicoverpa spp·);棉花實夜蛾屬（Heliothis spp·);小菜蛾（Plutella xylostella);直紋稻弄蝶 (Parnara guttata);衣蛾（Tinea translucens);衣蛾 (Tineola bisselliella)等。 雙翅目（Diptera): 、 庫蚊屬（CWex spp.) ’例如淡色庫蚊（cdex 〇 及三斑家蚊（CiiJex tritae_nio_r/27nc/ii/s);斑蚊屬 (Zedes spp·) ’例如埃及斑蚊（yledes ae幻φίί)及白線斑蚊 Uec/es ;按蚊屬（hop/jdes spp.)，例如中 華瘧蚊U/JopAeies sheflsis);搖蚊科（Chironomidae); 豕繩科（Muscidae) ’例如普通家繩（勤sea do/sestica)、廄 腐绳（Muscina stabulans)及（Fannia canicuhris);氣绳 科（Calliphoridae);麻蠅科（Sarcophagidae);花蠅科 (Anthomyiidae) ’ 例如種蠅（ieh'apJati/ra)及蒽蠅（i)eh.a afliigua);果實繩科（Tephritidae);潛繩科 320738 200932723 (Agromyzidae) ’ 果罐科（Dr0S0phiiidae) ’·蛾蚋科 (Psychodidae)，蚤罐科（ph〇ridae) ; it科（Tabanidae); 蚋科（Simuliidae) ’ 螯繩科（st〇m〇xyidae);蠓科 (Ceratopogonidae);等。 蜚蠊目（Blattaria)V - Ο 德國蜚蠊C^atteUa ger/Ba/jica);黑胸大蠊 (Periplaneta fuliginosa);美洲蜚螓（Periplaneta a/nericana)，掠色蜚蠊（PeWp/afleta ;東方蜚蠊 (Blatta oriental is);等。 膜翅目（Hymenoptera): 蟻科（Formicidae);胡蜂科（Vespidae);腫腿蜂科 (Bethylidae);葉蜂科（Tenthredinidae)，例如油菜葉蜂 CAthalia rosae ruficornis) ·，蓴。 蚤目（Siphonaptera):. 欠蛋（Ctenocephalides canis) ·，貓蚤 ❹(Ctenocephalides felis) .，人蚤(JPulex irritans).，等。 蟲目（Anoplura): ^KPediculus humanus).，德蝨（Pthirus pubis).， 頭蝨（Pec^CL/hs capitis);體蝨（PedicuJus corporis); 等' 等翅目（Isoptera): 黃胸散白蟻i iannes speratus);臺灣家白蟻 CCoptotermes formosanus) ’，等。 半翅目（Hemiptera): 12 320738 200932723 飛兹科（Delphacidae)，例如斑飛蟲（LaodeipAaz sthatenus)、褐飛蟲（见Haparvata •/[/获仍）及白背飛蟲 (Sc^atena _fi/i*ci/era);浮塵子科（Deltocephalidae)， 例如二點黑尾葉輝（iVep乃oieίί!·z yiresce/is)及黑尾葉蟬 (Wep/joteim ciflcticeps);財科（Aphididae);椿科 (Pentatomidae);粉蟲科（Aleyrodidae);軟介殼蟲科 , (Coccoidea);臭蟲科（Cimicidae)，例如溫帶臭蟲（Ci/nex Jecii/larit/s);軍配蟲科（Tingidae);木益科 Ο (Psyl1idae);等。 顆翅目（Coleoptera): 黑毛皮橐（^4打3公6卯5仙』七0_/〇1'&gt;/即0/2!'(^5);小圓皮 蠹（iiit/Lre/ms verfcasci);玉米食根蟲（Corn Rootwarms)， 例如玉米根葉曱（i)i a办ro ti ca Wrgi /era )及Η —星瓜葉甲 (Diabrotica iz/ideci/Hpiz/Jctata howardi);金龜子科 (Scarabaeidae)，例如金銅金龜（y4/2〇ffia〗a ct/prea)及榛姬The oxime reaction is carried out by reacting a compound (4) of a compound of the formula (4) (for example, grass-brewed chlorine) with a reaction of ammonia. On the ship, it is often in (four). An example of a solvent for the reaction is an ether solvent such as tetrahydro Dfu. The amount of the chlorinating agent used in the reaction is theoretically 1 mole relative to the compound of the formula (4), and the value may suitably be in the range of 1 mole to 3 moles, and preferably 1 mole to 3 moles. Choose within the scope. The chelating compound of the formula (4) can be reacted with a chlorinating agent in the presence of a base, if necessary. Examples of tests include triethylamine and bites. The reaction of the compound of the formula (4) with a chlorinating agent is usually carried out for 24 hours. The reaction temperature is usually hydrazine. (^至5〇°c. The reaction with ammonia is usually carried out by injecting ammonia gas or ammonia water into the reaction mixture of the above step or its concentrate. Relative to the compound of each mole type (4), ammonia The amount is theoretically 丨mol, but may be suitably selected from 1 mole to excess, and preferably from 1 mole to 3 moles. The reaction time for the reaction with ammonia is usually from 1 to 24 hours' The reaction temperature is usually 〇〇c to 5 (TC. 〇320738 200932723 After the reaction is completed, the compound of the formula (5) can be isolated, for example, by subjecting the reaction mixture to a conventional operation (for example, pouring the reaction mixture into the reaction mixture) The reaction is carried out in water, followed by extraction with an organic solvent and further concentration. Reaction from a compound of formula (5) to a compound of formula (6) is carried out by reacting a compound of formula (5) with acetic anhydride The amount of acetic anhydride used in the reaction is in the range of 5 moles to the excess per 1 mole of the compound of the formula (5). The reaction time of the reaction is usually in the range of 1 to 24 hours. The reaction enthalpy temperature is usually between 25 ° C and reflux of acetic anhydride. Within the range of the degree. After the completion of the reaction, the compound of the formula (6) may be isolated, for example, by subjecting the reaction mixture to a conventional operation (for example, pouring the reaction mixture into water, followed by extraction with an organic solvent and further concentration) And by isolation, if necessary, the isolated compound of formula (6) obtained by chromatography is purified by chromatography. The compound of formula (4) can be, for example, according to jp 2001-278851 A The method is prepared by appropriately purifying the obtained chrysanthemic aCid, or can be obtained by the filtrate obtained by the purification method according to the optical resolution method described in jP U-279111 A. Examples of pests that are effective include harmful arthropods such as harmful insects and harmful insects. Specific examples of such harmful arthropods are as follows. Le^idoptera: Pyralidae, such as Chilo suppressalis Moth (Chilo uppressalis), rice leaf curling wild moth (cnaphai〇cr〇cis 10 320738 200932723 1^(1111&amp;113) and Indian valley powder moth (?1〇(^3 111士6印11110^6113); Noctuidae Ae) ' For example, spodoptera litura, Pseudaletia separata, and Mamestra brassicae; Pieridae, such as Pieris rapaecrucivora; Tortricidae, for example, small Adoxophyes spp.; Carposinidae; Lyonetiidae; Lymantriidae; Autographa; Agrothis spp., such as Turnipus Agrotis segetum and Agrotis ipsilon; Helicoverpa spp.; Heliothis spp.; Plutella xylostella; Parrota (Pornara) Guttata); Tinea translucens; Tineola bisselliella and the like. Diptera (Diptera): , CWex spp. 'For example, Culex pipiens pallens (Cdex 〇 and Trichomonas vaginalis (CiiJex tritae_nio_r/27nc/ii/s); Aedes genus (Zedes spp·) 'eg Aedes ae illus φίί and Uec/es, Anopheles genus (hop/jdes spp.), such as U/JopAeies sheflsis; Chironomidae; Muscidae ) 'For example, the common house rope (Dragon sea do/sestica), Muscina stabulans and (Fannia canicuhris); the gas rope family (Calliphoridae); the genus Sarcophagidae; the Anthomyiidae ' (ieh'apJati/ra) and scorpion fly (i) eh.a afliigua); fruit genus (Tephritidae); submarine family 320738 200932723 (Agromyzidae) 'Dr0S0phiiidae' · Psychodidae, 〇 蚤 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Blattaria V - Ο German 蜚蠊C^atteUa ger/Ba/jica); Periplaneta fuliginosa; Periplaneta a/nericana, PeWp/afleta; Blattta oriental is; et al. Hymenoptera: Formicidae; Vespidae; Bethylidae; Tenthredinidae, such as the cane CAthalia Rosae ruficornis) ·, 莼. Siphonaptera: Ctenocephalides canis, Ctenocephalides felis, JPulex irritans, etc. Anoplura: ^KPediculus humanus)., Pthirus pubis., Pec^CL/hs capitis; PedicuJus corporis; etc. Isoptera: Yellow-breast Termite i iannes speratus); Taiwanese termite CCoptotermes formosanus) ', etc. Hemiptera: 12 320738 200932723 Delphacidae, such as Laodeip Aaz sthatenus, brown bug (see Haparvata •/[/ still) and white-backed worm (Sc^atena _fi/ i*ci/era); Deltocephalidae, such as two black-tailed leaves (iVep is oieίί!·z yiresce/is) and black-tailed spider mites (Wep/joteim ciflcticeps); Aphididae; Pentatomidae; Aleyrodidae; Coccoidea; Cimicidae, such as temperate bed bugs (Ci/nex Jecii/larit/s); Tingidae; Psyl1idae; et al. Coleoptera: Black fur 橐 (^4 打 3 公6卯5仙』七0_/〇1'&gt;/即0/2!'(^5); 小圆皮蠹(iiit/Lre/ Ms verfcasci); Corn rootwarms, such as the corn root leaf 曱 (i) ia do ro ti ca Wrgi /era ) and Η - bro 星 星 (Diabrotica iz / ideci / Hpiz / Jctata howardi); chafer Scarabaeidae, such as gold and copper tortoise (y4/2〇ffia a ct/prea) and Yu Ji

I ❿ 金龜（2/2〇/z/a 7a ru/ocuprea);象鼻蟲科（Cur cu lion idae)， 例如玉米象（Si ίορ/ii/t/s zea/nais)、稻水象甲 (Lissorhoptrus oryzophilus) ' (Anthonomus grandis grandis)反綠豆象（Callosobruchus c/n’/je/isis);擬步曱科（Tenebrionidae)，例如黃粉蟲 (Tenebrio molitor)反赤毅敦KTribolim castaneum) ·， 金花蟲科（Chrysomelidae)，例如稻負泥蟲（OuJe/na oryzae)、黃條葉蚤（jP/^iioireia strio_/aia)及黃守瓜 (ii^acophora /eisoraJis);竊橐科（Anobiidae);食植瓢 13 320738 200932723 義屬（Epilachna ，例如茄二十八I瓢螽（Epilachna yi^i/jiiociopMciaia);粉蠹科（Lyctidae);長蠹科 (Bostrychidae);天牛科（Cerambycidae);蟻形隱翅蟲 iPaederus fuscipes).，蓴。 纓翅目（Thysanoptera): 瓜薊馬（77]rips paki);西方花薊馬 &gt; occidentals) ·，花薊馬（Thrips hawaiiensis);等。 ^ 直翅目（Orthoptera): 螻蛄科（Gryllotalpidae);蝗科（Acrididae);等。 蜱蜗目（Acarina): 塵蟎科（Pyroglyphidae) ’例如美洲塵蜗 (Dermatophagoides farinae)反跋洲塵編 (Dermtophagoides pteronyssinus) ·，粉蟎科 (Acaridae) ’ 例如腐食酷蜗（Tyrophagi/s pzitrescefliiae) 及橢圓食粉蟎（heurc^iyp/iiis ovairi/s);食甜蟎科 〇 (Glycyphagidae)，例如隱秘甘嗜蟠（67ycypAapis priFaius)、家食甜蟎（G7ycyp/2agt/scio/0esiicL/s)及食甜蜗 (67ycyp/2agusdesiri/cior);肉食蟎科（Cheyletidae)，例 如馬六甲肉食蟎iHaJacceflsis)及肉食蜗 (C/3ey_/et：us /ortis);細蜗科（Tarsonemidae);嗜渣端屬 (i：/}〇riog7yp/u/s spp.);地蟎超科（OHbatei);葉蟎科 (Tetranychidae)，例如二斑葉蜗（T'etra/jyc/jt/s tzrii'cae)、神澤葉蟎（Teira即c/u/s 、柑桔全爪 蛾（Panonychus citri)及榆全爪蟎（panonychus ulmi) ' 硬 320738 200932723 蜱科（Ixodidae)，例如長角血蜱（/TaefflapAysaJis ;皮刺蟎科（Dermanyssidae)，例如禽刺蟎 (Orni thonyssus sylviarum)及雞皮剌瞒（Dermanyssus gallinae') ·，專。 本發明之害蟲防治組成物可為本發明化合物本身，但 通常調配成下列調配物形式。該調配物之實例包含油性溶 液、可乳化濃縮物、可渔性粉末、可流動性調配物（例如水 懸浮液及水性乳液）、微膠囊、粉劑、粒劑、錠劑、氣霧劑、 〇 二氧化碳調配物、熱散發式調配物（例如殺蟲燦香劑 (pesticidal incense)、電殺蟲片（electric pesticidal mat)及液體吸收芯型熱散發式殺蟲劑（liquid absorbing core-type heat transpiration pesticide)、壓力式殺蟲 調配物、熱燻蒸劑（例如自燃型燻蒸劑、化學反應型燻蒸劑 及多孔陶瓷板燻蒸劑）、非熱散發式調配物（例如樹脂散發 式調配物、紙散發式調配物、不織布散發式調配物、織物 ❹ 散發式調配物及昇華錠（sublimating tablet))、喷霧劑調 配物（例如煙霧劑調配物）、直觸型調配物（例如片狀接觸式 調配物、條狀接觸式調配物及網狀接觸式調配物）、ULV調 配物及毒_ 〇 調配方法之實例係如下列者。 (1) 一種方法，包括將本發明化合物與固體載劑、液體載 劑、氣體載劑或毒餌混合，接著加入界面活性劑及用 於調配物之其他輔助劑，若有需要，則進一步加工。 (2) —種方法’包括將本發明化合物含浸於不含活性成分 15 320738 200932723 之基料中。 (3) —種方法，包括 混合物進行模製=本螯明化合物和基料混合，接著使 這些調配物通常含 物，惟該用量依調配物私.001至98重«之本發明化合 土、矽藻土、膨潤土、々栽劑之實例包含黏土（例如高嶺 白黏土）之細粉末或顆教$、1沙黏土（Fubasami clay)及酸性 其他無機礦物（例如絹雲成丨生水5氧化發、滑石、陶瓷、 水合氧化矽）及化學肥料石英、硫、活性碳、碳酸鈣及 ^例如硫酸銨、磷酸 氣化銨及脲）；在室溫為固體之㈣⑴/録为酸按 勹u體之物質（例如2,4,6_三異丙基 -1，3’5-三曙烧、萘、對二氯笨、樟腦及金剛石）；以及熟 製品、'纖維、布料、織物、薄片、紙、線狀物、泡床、多 孔性材料及複絲（multi-filament)，其各包括一種或多種 選自羊毛、絲、棉、麻、紙漿、合成樹脂、玻璃、金屬及 ❹ 陶瓷之物質。 用於固體載劑之合成樹脂之實例包含聚乙烯樹脂，例 如低密度聚乙烯、直鏈低密度聚乙烯及高密度聚乙烯；乙 烯-乙烯酯共聚物，例如乙烯-醋酸乙烯酯共聚物；乙烯一 甲基丙烯酸酯共聚物，例如乙烯-甲基丙烯酸甲酯共聚物及 乙烯-甲基丙烯酸乙酯共聚物；乙烯_丙烯酸酯共聚物，例 如乙烯-丙烯酸甲酯共聚物及乙烯-丙烯酸乙酯共聚物；乙 烯-乙烯基羧酸共聚物，例如乙烯-丙烯酸共聚物；乙烯一 四環十二婦共聚物，聚丙浠樹脂，例如丙埽均聚物及丙稀_ 320738 16 200932723 ' 乙烯共聚物；聚-4-曱基戊烯-l(poly-4-methylpentene -1)、聚丁婦_l(P〇lybutene-l)、聚丁二婦、聚苯乙烯；丙 烯腈-苯乙烯樹脂；丙烯腈-丁二烯-苯乙烯樹脂；苯乙烯彈 性體，例如苯乙烯-共軛二烯嵌段共聚物及氫化苯乙烯-共 軛二烯嵌段共聚物；氟樹脂；丙烯酸系樹脂，例如聚甲基 丙烯酸甲酯；聚醯胺樹脂，例如尼龍6(nyIon 6)及尼龍66 (nylon 66);聚酯樹脂，例如聚對苯二曱酸乙二酯、聚萘 二甲酸乙二酯、聚對苯二甲酸丁二酯及聚對苯二甲酸伸環 ❺ 己基二亞曱醋（P〇lycyclohexylene dimethylene terephthalate);及多孔性樹脂，例如聚碳酸酯、聚縮醛、 聚丙烯颯（polyacryl sulfone)、聚丙烯酸酯、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、 聚偏二氯乙烯、聚胺酯、聚胺酯泡沫、聚丙烯泡沫及乙烯 泡珠。 液體載劑之實例包含芳香族烴類或脂肪族烴類（例如 ❹二曱苯、甲苯、烷基萘、苯基二曱笨基乙烷、煤油、輕油、 己烷及環己烧）、鹵化烴類（例如氣苯、二氯曱烷、二氯乙 烷及三氯乙烷）、醇類（例如曱醇、乙醇、異丙醇、丁醇、 己醇、苯.甲醇及·乙·一醇）、驗類（例如二乙.鍵、乙二醇二甲 醚、二乙二醇單曱醚、二乙二醇單乙醚、丙二醇單曱醚、 四氫呋喃及二噚烷）、酯類（例如醋酸乙酯及醋酸丁酯）、酮 類（例如丙酮、甲基乙基酮、甲基異丁基酮及環己酮）、腈 類（例如6腈及異丁腈）、亞礙類（例如二甲基亞颯）、羧醯 胺類（acid amides)(例如N，N-二甲基甲醯胺、N，N_二曱基 17 320738 200932723 乙醯胺及N-甲基-吡咯啶酮）、碳酸烷二酯（例如碳酸丙二 酯）、植物油類（例如大豆油及棉籽油）、植物精油類（例如 橙油、海索油（hyssop oil)及檸檬油）及水。 氣體載劑之實例包含丁烷氣體、氟氯化碳、液化石油 氣(LPG)、二曱醚、二氧化碳。I ❿ Golden tortoise (2/2〇/z/a 7a ru/ocuprea); Cur cu lion idae, such as corn elephant (Si ίορ/ii/t/s zea/nais), rice water weevil (Lissorhoptrus oryzophilus) ' (Anthonomus grandis grandis) anti-mung bean (Callosobruchus c/n'/je/isis); Tenebrionidae, such as Tenebrio molitor, KTribolim castaneum), Chrysomelidae, such as OuJe/na oryzae, jP/^iioireia strio_/aia, and ii^acophora/eisoraJis; Anobiidae ); food planting scoop 13 320738 200932723 genus (Epilachna, for example, Epilachna yi^i/jiiociopMciaia; Lyctidae; Bostrychidae; Cerambycidae) ; ant-shaped stag beetle iPaederus fuscipes)., 莼. Thysanoptera: 蓟 蓟 (77) rips paki); western flower 蓟 horse &gt; occidentals) ·, Thrips hawaiiensis; ^ Orthoptera: Gryllotalpidae; Acrididae; et al. Acarina: Pyroglyphidae 'For example, Dermatophagoides farinae, Dermtophagoides pteronyssinus ·, Acaridae', eg Tyrophagi/s pzitrescefliiae And elliptic meal meal (heurc^iyp/iiis ovairi/s); Glycyphagidae, such as 67ycypAapis priFaius, G7ycyp/2agt/scio/0esiicL/s Sweet worm (67ycyp/2agusdesiri/cior); Cheyletidae, such as Malacca meat 螨iHaJacceflsis) and carnivorous snail (C/3ey_/et:us /ortis); Tarsonemidae; slag-end Genus (i:/}〇riog7yp/u/s spp.); OH 螨 螨 (OHbatei); tran 螨 (Tetranychidae), such as the two-spotted snail (T'etra/jyc/jt/s tzrii'cae) , 泽泽叶螨 (Teira ie c/u/s, citrus full claw moth (Panonychus citri) and 榆 榆 pan (panonychus ulmi) 'hard 320738 200932723 x科 (Ixodidae), such as long-horned blood 蜱 (/TaefflapAysaJis Dermanyssidae, such as Orni thonyssus sylviarum and Goosebump (Dermanyssus) Gallinae') The pest control composition of the present invention may be the compound of the present invention itself, but is usually formulated into the following formulation forms. Examples of the formulation include an oily solution, an emulsifiable concentrate, a fishable powder, and the like. Fluid formulations (eg, aqueous suspensions and aqueous emulsions), microcapsules, powders, granules, lozenges, aerosols, hydrazine carbon dioxide formulations, heat-distributing formulations (eg, pesticidal incense) , electric pesticidal mat and liquid absorbing core-type heat transpiration pesticide, pressure insecticidal formulation, thermal fumigant (eg pyrophoric fumigant, chemistry) Reactive fumigants and porous ceramic plate fumigants), non-thermal emission formulations (eg resin-dispersed formulations, paper-spreading formulations, non-woven sporadic formulations, fabrics, sporadic formulations, and sublimating tablets) )), spray formulations (eg aerosol formulations), direct-touch formulations (eg sheet contact formulations, strip contacts) Formulations and net-like contact formulations), ULV the method of the Example formulations and drug formulations were adjusted _ those following lines such as square. (1) A method comprising mixing a compound of the present invention with a solid carrier, a liquid carrier, a gaseous carrier or a poison bait, followed by addition of a surfactant and other adjuvants for the formulation, and further processing if necessary. (2) A method 'includes impregnation of a compound of the invention in a base material free of active ingredient 15 320738 200932723. (3) A method comprising: molding a mixture = mixing the present chelate compound with a binder, and then subjecting the formulation to a usual content, except that the amount is from 001 to 98% by weight of the compound of the present invention, Examples of diatomaceous earth, bentonite, and sorghum include fine powder of clay (for example, kaolin white clay) or shovel of $1, Fubasami clay, and other acidic minerals such as sputum. Talc, ceramics, hydrated cerium oxide) and chemical fertilizers quartz, sulfur, activated carbon, calcium carbonate and ^such as ammonium sulfate, ammonium phosphate and urea); solid at room temperature (4) (1) / recorded as acid Substances (eg 2,4,6_triisopropyl-1,3'5-triazine, naphthalene, p-dichlorobenzene, camphor and diamond); and cooked products, 'fibers, fabrics, fabrics, flakes, paper A thread, a bubble bed, a porous material, and a multi-filament each comprising one or more materials selected from the group consisting of wool, silk, cotton, hemp, pulp, synthetic resin, glass, metal, and enamel. Examples of the synthetic resin used for the solid carrier include polyethylene resins such as low density polyethylene, linear low density polyethylene, and high density polyethylene; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer; ethylene Monomethacrylate copolymers such as ethylene-methyl methacrylate copolymer and ethylene-ethyl methacrylate copolymer; ethylene acrylate copolymers such as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate Copolymer; ethylene-vinyl carboxylic acid copolymer, such as ethylene-acrylic acid copolymer; ethylene tetracyclotetraodecan copolymer, polypropylene resin, such as propylene homopolymer and propylene _ 320738 16 200932723 'ethylene copolymer ; poly-4-methylpentene-1 (poly-4-methylpentene-1), polybutylene-l (P〇lybutene-l), polybutanin, polystyrene; acrylonitrile-styrene resin; Acrylonitrile-butadiene-styrene resin; styrene elastomer such as styrene-conjugated diene block copolymer and hydrogenated styrene-conjugated diene block copolymer; fluororesin; acrylic resin, for example Polymethyl methacrylate Indoleamine resins, such as nylon 6 (nyIon 6) and nylon 66 (nylon 66); polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate And polybutylene terephthalate (P〇lycyclohexylene dimethylene terephthalate); and porous resin, such as polycarbonate, polyacetal, polyacryl sulfone, polyacrylate, hydroxybenzene Formic acid polyester, polyether phthalimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, polyurethane foam, polypropylene foam and vinyl beads. Examples of the liquid carrier include aromatic hydrocarbons or aliphatic hydrocarbons (for example, anthraquinone, toluene, alkylnaphthalene, phenyldiazepine, kerosene, gas oil, hexane, and cyclohexane), Halogenated hydrocarbons (eg, benzene, dichlorodecane, dichloroethane, and trichloroethane), alcohols (eg, decyl alcohol, ethanol, isopropanol, butanol, hexanol, benzene, methanol, and B) Monool), test (such as diethyl bond, ethylene glycol dimethyl ether, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, propylene glycol monoterpene ether, tetrahydrofuran and dioxane), esters ( For example, ethyl acetate and butyl acetate), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone), nitriles (such as 6 nitrile and isobutyronitrile), sub-obstructions ( For example, dimethyl hydrazine), acid amides (eg, N,N-dimethylformamide, N,N-didecyl 17 320738 200932723 acetamide and N-methyl-pyrrolidine Ketone), alkylene carbonate (such as propylene carbonate), vegetable oils (such as soybean oil and cottonseed oil), plant essential oils (such as orange oil, hyssop oil and lemon) Oil) and water. Examples of gaseous carriers include butane gas, chlorofluorocarbon, liquefied petroleum gas (LPG), dioxane, carbon dioxide.

界面活性劑之實例包含硫酸烧基酯鹽類、烷基磺酸酯 鹽類、·烧基方基續酸酯鹽類、烧基芳基鱗類、聚氧伸.乙基 北烧基芳基越類（polyoxyethylenated alkylary 1 ethers)、聚乙二醇醚類、多元醇酯類、及糖醇衍生物。 用於調配物之其他辅助劑之實例包含黏結劑、分散劑 及女疋劑。具體言之’該等輔助劑為例如’路蛋白、明膠、 醣類（例如澱粉、阿拉伯膠、纖雉素衍生物及藻酸）、木質 素衍生物、膨潤土、蔗糖、合成之水溶性聚合物（例如聚乙 婦醇及聚乙烯吡咯啶酮）、聚丙烯酸、BHT(2, 6-二第三丁基 一4-甲基酚）及βΗΑ(2·“第三丁基-4-甲氧基酚與3-第三丁基 一4-甲氧基酚之混合物）。 用於殺蟲燻香劑&lt;基料之實例包含植物粉末（例如木 粉及酒糟粉（lees powder))以及黏結劑（例如燦香材料粉 末、澱粉及麩質）之混合物。 刀 用於電殺蟲片之基料之實例包含硬化成平板狀之棉 絨及硬化成平板狀之棉絨與紙衆的混合物之細纖維。 、，自燃型燻蒸劑之基料之實例包含可燃的發熱劑，例如 硝酸鹽、亞硝酸鹽、胍鹽、氯酸鉀、硝化纖維素、乙基纖 維素及木粉；熱分解促進劑，例如鹼金屬鹽、鹼土金屬鹽、 320738 18 200932723 重鉻酸鹽及鉻酸鹽；載氧劑，例如硝酸钟；助燃劑，例如 三聚氰胺及粉狀殿粉；增量劑（extender)，例如;s夕蕩土； 及黏結劑，例如合成膠。 用於化學反應型燻蒸劑之基料之實例包含發熱劑，例 如鹼金屬硫化物、多硫化物、疏氫化物及氧化鈣；催化劑’ 例如碳_質材料、碳化鐵及活性白黏土；有機發泡劑，例如 偶氮二甲醯胺、苯磺醯肼、，二硝基五亞甲基四胺 ❹（dinitropeniamethylenetetramine)、聚笨乙烯及聚胺 醋；及填料，例如天然纖維及合成纖維之條帶。 用於樹脂散發式調配物之基料之實例包含聚乙烯樹 脂’例如低密度聚乙烯、直鏈低密度聚乙烯及高密度聚乙 婦；乙烯-乙烯酯共聚物，例如乙烯-醋酸乙稀酯共聚物； 乙歸-曱基丙烯酸酯共聚物，例如乙烯—甲基丙烯酸曱酯共 聚物及乙烯-曱基丙烯酸乙酯共聚物；乙烯—丙烯酸醋共聚 物’例如乙烯-丙烯酸曱酯共聚物及乙烯-丙烯酸乙酯共聚 © 物；乙稀-乙烯基羧酸共聚物，例如乙烯_丙烯酸共聚物； 乙稀-四環十二烯共聚物；聚丙烯樹脂，例如丙烯共聚物及 丙烯-乙烯共聚物；聚_4_曱基戊烯_丨、聚丁烯—丨、聚丁二 烯、聚苯乙烯；丙烯腈-苯乙烯樹脂；丙烯腈-丁二烯-苯乙 婦樹脂；苯乙烯彈性體，例如苯乙烯_共軛二烯嵌段共聚物 及氯化苯乙烯-共軛二烯嵌段共聚物；氟樹脂；丙烯酸系樹 月曰’例如聚甲基丙烯酸甲酯；聚醯胺樹脂，例如尼龍6及 尼龍66 ;聚酯樹脂，例如聚對苯二曱酸乙二酯、聚萘二甲 酸乙二醋、聚對苯二曱酸丁二酯及聚對苯二甲酸伸環己基 19 320738 200932723 、二亞甲酯；聚碳酸酯、聚縮醛、聚丙烯颯、聚丙烯酸酯、 經，苯甲酸《、聚醜亞胺、聚§旨碳酸g|、聚苯謎樹脂、 聚氯乙烯、聚偏二氯乙烯及聚胺酯。，這些基料可單獨使用， 或組合其兩種或更多種使用。若有需要，可於這些基料中 • 添^塑化劑，例如鄰苯二甲動旨（例如鄰苯二甲酸二甲醋及 鄰苯二曱酸二辛醋）、己二酸酉旨及硬脂酸。該樹脂散發式調 配物係經由將本發明化合物與上述基料混合，揉捏混合 ❹物，接著再將混合物經由射出成型、擠壓成型或模壓成型 來模製而製彳于。若有需要，所得樹脂調配物可進一步經由 ,製或切割步驟而加工成平板、薄膜、條冑、網狀或細繩 等形狀。這些樹脂調配物係加工成動物頸圈、動物耳標、 片狀乂 誘引繩、園藝樁柱（gardening supports)及其 他產品。 、用於毒餌之基料之實例包含食品配料，例如榖粉、植 — 酶類及結晶纖維素；抗氧化劑，例如二丁基經基甲 ❹苯及降一氫癒創木酸（n〇rd i dr〇gua丨ar e t丨c . 如去氳乙酸；防止兒童及寵物誤食之抑制劑，’例如 、’ ^，誘引昆蟲之香料，例如乳酪香料、洋蔥香料及花 本發明之害蟲防治方法係經由將有效量之本發明化名 物（通常以本發明之害蟲防治組成物之形式）施 其棲息處而進行。 一 本發明之害蟲防治組成物之施用方法係根據組成物形 式及欲使用之區域而予以適當地選擇。例如，採用下列方 320738 20 200932723 法。 (1) 一種方法，包括將呈原 成物麵至害蟲或該害^棲組 (2) —種方法，包括將本發 如水)稀釋，然後再將，1害蟲防治組成物以_^^ 該害蟲之棲息處 經稀釋之組成物噴佈至害蟲或 ❹ Ο 可乳(其通常係調配成 至 =配_稀釋而使本發二二= 1U,000 ppm ° ⑶種方法’包括在害蟲之棲息處加熱本發明之害 治組成物，以使活性成分揮發及擴散。 σ 此方法中，欲施用之本發明化合物之用量及 據其形式、施用時斯、施用區域、施用方法、害蟲種類根 所導致之傷害及其他因素而適當地決定。 用於防治流行病之本發明化合物之用量在將其施甩於 空間時通常為0.0001至1000 mg/m3。在將其施用於平面時 之用量則為0.0001至1，〇〇〇 mg/m2。殺蟲燻香劑或電殺蟲 片係根據其形式來加熱以使活性成分揮發及擴散而施用。 樹脂散發式調配物、紙散發式調配物、木織布散發式調配 物、織物散發式調配物或昇華錠係透過將其置於歌施用之 空間、或透過將其放於氣流中而施用。 用於防治流行病而施用本發明之害蟲防治組成物之空 間之實例包含壁櫥、廚台、衣櫃、箱櫃、食櫃、洗手間、 3^〇73g 21 200932723 々至H起居室、餐廳、車庫和汽車内部。本發明組 成物亦可施用於戶外空地。 ' 田本發明之害蟲防治組成物係用於家畜（例如牛、馬、 豬、’名羊山羊及雞）及小型動物（例如狗、貓、大鼠及小 执）以達則U卜寄生蟲之目的時，可對該等動物應用獸醫 ，7貞域中已去的方法。具體言之，當欲用於全身性防治時， 該調配物係藉由竣劑、倒料混合物、检劑及注射劑（包含肌 〇内庄射、皮下注射、靜脈内注射及腹腔内注射）之方式投 予另方面，當欲用於非全身性防治時，該調配物係藉 由喷灑油H/谷液或水性溶液、洗注（_r_Qn)處理或滴注 (spot-on)處理、以洗髮精調配物來洗滌動物、或將樹脂調 配物製成的頸圈或耳標安裝於動物之方式來使用。本發明Examples of the surfactant include a sulfuric acid alkyl ester salt, an alkyl sulfonate salt, a pyridyl sulfonate salt, a aryl aryl sulphate, a polyoxyl extension, an ethyl melamine aryl group. Polyoxyethylenated alkylary 1 ethers, polyethylene glycol ethers, polyol esters, and sugar alcohol derivatives. Examples of other adjuvants for the formulation include a binder, a dispersing agent, and a licking agent. Specifically, the adjuvants are, for example, 'road proteins, gelatin, sugars (such as starch, gum arabic, fibrin derivatives and alginic acid), lignin derivatives, bentonite, sucrose, synthetic water-soluble polymers. (e.g., polyethyl alcohol and polyvinylpyrrolidone), polyacrylic acid, BHT (2,6-di-t-butyl-4-methylphenol), and βΗΑ(2·“t-butyl-4-methoxy Mixture of phenol and 3-tert-butyl-4-methoxyphenol). Examples of insecticidal incense agents &lt;bases include plant powders (such as wood flour and lees powder) and bonding Mixtures of agents (for example, powders of scented material, starch and gluten). Examples of knives used as bases for electric insecticide tablets include a mixture of cotton linters hardened into a flat shape and hardened into a flat shape. Examples of the base of the fine fiber., self-igniting fumigant include a flammable heat generating agent such as nitrate, nitrite, strontium salt, potassium chlorate, nitrocellulose, ethyl cellulose and wood powder; thermal decomposition accelerator, For example, alkali metal salts, alkaline earth metal salts, 320738 18 200932723 dichromate Chromate; oxygen carrier, such as nitric acid clock; combustion improver, such as melamine and powdered powder; extender, for example; sauer; and binder, such as synthetic rubber. Examples of the base of the fumigant include a heat generating agent such as an alkali metal sulfide, a polysulfide, a sulfonated hydride, and a calcium oxide; a catalyst such as a carbonaceous material, iron carbide, and an active white clay; an organic foaming agent such as an even Nitromime, benzenesulfonamide, dinitropeniamethylenetetramine, polystyrene and polyurethane; and fillers, such as natural fibers and synthetic fibers. Examples of the base of the sporadic formulation include a polyethylene resin such as low density polyethylene, a linear low density polyethylene, and a high density polyethylene; an ethylene-vinyl ester copolymer such as an ethylene-vinyl acetate copolymer; Ethylene-mercapto acrylate copolymer, such as ethylene-methyl methacrylate copolymer and ethylene-ethyl methacrylate copolymer; ethylene-acrylic acid vinegar copolymer, such as ethylene-acrylic acid acrylate And ethylene-ethyl acrylate copolymer © Ethylene-vinyl carboxylic acid copolymer, such as ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymer; polypropylene resin, such as propylene copolymer and propylene - Ethylene copolymer; poly_4_decylpentene-丨, polybutene-fluorene, polybutadiene, polystyrene; acrylonitrile-styrene resin; acrylonitrile-butadiene-benzene-ethylene resin; benzene a vinyl elastomer such as a styrene-conjugated diene block copolymer and a chlorinated styrene-conjugated diene block copolymer; a fluororesin; an acrylic tree such as polymethyl methacrylate; Amine resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, butylene dibutyl phthalate and polybutylene terephthalate己基19 320738 200932723, Dimethyl ester; Polycarbonate, Polyacetal, Polypropylene, Polyacrylate, benzoic acid, uglyimine, poly-glycol g |, polyphenylene resin, poly Vinyl chloride, polyvinylidene chloride and polyurethane. These base materials may be used singly or in combination of two or more kinds thereof. If necessary, add plasticizers to these bases, such as phthalate (such as dimethyl phthalate and phthalic acid dioctyl vinegar), adipic acid Stearic acid. The resin-dispersed formulation is prepared by mixing the compound of the present invention with the above-mentioned base, kneading the mixture, and then molding the mixture by injection molding, extrusion molding or compression molding. If desired, the resulting resin formulation can be further processed into a shape such as a flat sheet, a film, a strand, a mesh or a string by a manufacturing or cutting step. These resin formulations are processed into animal collars, animal ear tags, flaky sputum attracting ropes, gardening supports and other products. Examples of base materials for baits include food ingredients such as tantalum powder, phyto-enzymes and crystalline cellulose; antioxidants such as dibutyl methacrylate and hydroxy-guaiac acid (n〇rd) i dr〇gua丨ar et丨c. Inhibition of indoleacetic acid; prevention of ingestion of children and pets, 'eg, '^, insect-inducing spices, such as cheese spices, onion flavors and flowers, the pest control method of the present invention It is carried out by applying an effective amount of the instant name of the present invention (usually in the form of the pest control composition of the present invention) to the habitat. The method for applying the pest control composition of the present invention is based on the form of the composition and the intended use. The area is appropriately selected. For example, the following method 320738 20 200932723 is used. (1) A method comprising the method of bringing the original object into the pest or the pest group (2), including the method of Diluting, and then, 1 pest control composition to _^^ The diluted composition of the pest's habitat is sprayed onto the pest or ❹ Ο milk (which is usually formulated to = _ dilution to make the hair Two two = 1U,000 ppm ° (3) Method 'includes heating the pesticidal composition of the present invention in the habitat of the pest to volatilize and diffuse the active ingredient. σ In this method, the amount of the compound of the present invention to be administered and according to its form, application time, The application area, the method of application, the damage caused by the roots of the pest species, and other factors are appropriately determined. The amount of the compound of the present invention for controlling an epidemic is usually 0.0001 to 1000 mg/m3 when it is applied to the space. When it is applied to a flat surface, it is used in an amount of 0.0001 to 1, 〇〇〇mg/m 2. The insecticidal or electric insecticidal tablet is heated according to its form to volatilize and diffuse the active ingredient. Formulations, paper-spreading formulations, wood-woven sporadic formulations, fabric-spreading formulations or sublimation ingots are applied by placing them in the space for song application or by placing them in a gas stream. Examples of the space for applying the pest control composition of the present invention to epidemics include closets, kitchen counters, wardrobes, cabinets, food cabinets, restrooms, 3^〇73g 21 200932723 々 to H living room, dining room, The interior of the library and the automobile. The composition of the present invention can also be applied to outdoor open spaces. 'The pest control composition of the invention is used for livestock (such as cattle, horses, pigs, 'male goats and chickens) and small animals (such as dogs). , cats, rats, and small stalks. For the purpose of U.sub. parasites, veterinarians can be used in these animals, and the methods have been used in the field. In particular, when used for systemic control, The formulation is administered to the other side by means of tincture, mixture of the mixture, test and injection (including intramuscular injection, subcutaneous injection, intravenous injection and intraperitoneal injection) when used for non-systemic control. In this case, the formulation is washed by spraying oil H/gu solution or aqueous solution, washing (_r_Qn) treatment or spot-on treatment, washing the animal with shampoo preparation, or formulating the resin. The finished collar or ear tag is used in an animal manner. this invention

化合物之劑量範圍通常係每1公斤（kg)動物體重為〇 〇1至 1000 毫克（mg) P 本發明之害蟲防治組成物可與一種戒多種其他殺昆蟲 ❹劑、殺蟎劑、殺線蟲劑、土壤害蟲防治劑、殺真菌劑、除 草劑、植物生長5周卽物質、拒避劑（repel lents)、增效劑、 肥料及土壤調理劑混合或組合使用。 用於殺昆蟲劑及殺蟎劑之活性成分之實例包含： 有機磷化合物類，例如敵敵畏（dichlorvos)、撲滅松 (fenitrothion)、氰乃松（Cyan〇ph〇s)、佈飛松 (profenofos)、硫丙磷（suiprof〇s)、赛達松 (phenthoate)、加福松（isoxathi〇n)、殺蟲畏 (tetrachlorvinphos)、芬殺松（fenthion)、陶斯松 22 320738 200932723 ， （chlorpyrifos)、大利松（diazinon)、毆殺松（acephate)、 托福松（terbufos)、福瑞松（phorate)、氯氧填 (chlorethoxyfos)、福賽絕（fosthiazate)、普伏松 (ethoprophos)、硫線碟（cadusafos)、滅大松 (methidathion)、二硫松（disulfoton)、水揚硫填 (dioxabenzofos)、大滅松（dimethoate)、赛達松 ， (phenthoate)、馬拉松（malathion)、三氯松 (trichlorphon)、谷速松（azinphos-methyl)、亞素靈 ® (monocrotophos)、愛殺松（ethion)等； 胺基甲酸酯化合物類’例如安丹（propoxur)、加保利 (carbaryl)、β惡蟲酮（metoxadiazQne)、仲丁威 (fenobucarb)、納乃得（methomyl)、硫雙威（thiodicarb)、 棉鈴成（alanycarb)、免扶克（benfuracarb)、歐殺滅 (oxamyl)、得滅克（aldicarb)、滅賜克（methiocarb)、丁 基加保扶（carbosulfan)、乙硫苯威（ethiofencarb)、芬硫 φ 克（fenothiocarb)、培丹（cartap)等； 類除蟲菊酯（pyrethroid)化合物類，例如亞列寧 (allethrin)、泰滅寧（tralomethrin)、普亞列寧 (pral lethrin)、d-苯謎菊酯（d-phenothrin)、d-異列滅寧 (d-resmethrin)、赛紛寧（cyphenothrin)、百滅寧 (permethrin)、赛滅寧（cypermethrin)、α-赛滅寧 (alpha-cypermethrin)、赛滅寧（zeta-cypermethrin)、第滅寧（deltamethrin)、四溴菊酯 (tralomethrin)、賽扶寧（cyfluthrin)、yS-賽扶寧 23 320738 i 200932723 (beta-cyfluthrin)、赛洛寧（cyhalothrin)、λ-赛洛寧 (lambda-cyhalothrin)、d-伏滅靈（d-furamethrin)、益普 靈（imiprothrin)、醚菊 S旨（ethofenprox)、芬化利 (fenvalerate)、益化利（esfenvalerate)、芬普寧 ‘ （fenpropathrin)、矽護芬（silafluofen)、畢芬寧 (bifenthrin)、拜富寧（transfluthrin)、護赛寧 (flucythrinate)、r -福化利（tau-f luvalinate)、阿納寧 (acrinathrin)、七氟菊酯（tefluthrin)、乙氰菊酯 Ο (cycloprothrin)、美特寧（metofluthrin)、丙氟菊酯 (profluthrin)、四氟甲醚菊酯（dimefluthrin)、益避寧 (empenthrin)、氟氯苯菊酯（f lumethrin)、福化利 (f luvalinate)、2-曱基-2-(4-溴二氟曱氧基苯基）丙基（3-苯氧基苯甲基）醚及2, 2, 3, 3-四曱基環丙烷羧酸5-(2-丙 炔基）呋喃甲酯； 新類尼古丁（neonicotinoid)化合物類，例如亞滅培 ❿（acetamiprid)、烯咬蟲胺（nitenpyram)、嘆蟲琳 (thiacloprid)、嗟蟲嗪（thiamethoxam)、達特南 (dinotefuran)、可尼丁（clothianidine)、益達胺 (imidacloprid)等； 氯化烴化合物類，例如.硫丹（endosu 1 f an )、γ-BHC及 1，1-雙（氯苯基）-2, 2, 2-三氯乙醇； 苯曱醯基苯基脲化合物類，例如祿芬隆（lufenuron)、 克福隆（chlorfluazuron)、六伏隆（hexailumuron)、除蟲 脲（diflubenzuron)、殺鈐脲（triflumuron)、得福隆 24 320738 200932723 (teflubenzuron)、氟芬隆（flufenoxuron)、氟咬碑脲 (fluazuron)、諾伐隆（novaluron)、三唾隆（triazuron)、 雙三氟蟲脲（bistrifluron)、氟芬隆（flufenoxuron)等； 青春激素（juvenile hormone)類似物類，例如百利普芬 (pyriproxyfen)、美賜年（methoprene)、烯蟲乙酯 (hydroprene)、雙氧威（phenoxycarb)等； 苯基β比峻化合物類，例如氟蟲腈（pyriprole)、丁稀氟 蟲腈（pyrafluprole)、乙蟲清（ethiprole)等； 苯甲驢肼化合物類，例如抑蟲肼（tebufenozide)、可 芬諾（chromafenozide)、滅芬諾（methoxyfenozide)、氯蟲 醯肼（halofenozide)等； 大環内酯物（macrolide)化合物類，例如萘菌素複合物 (polynactin complex)(四活菌素（tetranactin)、二活菌 素（dinactine)及三活菌素（trinactin))、阿維菌素 (abamectin)、齊螨素（avermectin)、因滅汀（emamectin ❹ benzoate)、賜諾殺（spinosad)、印楝素（azadirachtin)、 &gt; 密滅汀（milbemectin)等；及 丁鱗腺（diafenthiuron)、πϋ缉嗣（pymetrozine)、氟 咬蟲醯胺（flonicamide)、峻財威（triazamate)、布芬淨 (buprofezin)、賜諾殺（spinosad)、因滅汀（emamectin benzoate)、溴蟲清（chlorphenapyr)、因得克（indoxacarb MP)、咬蟲丙謎（pyridalyl)、滅繩胺（cyromazine)、芬普 蜗（fenpyroximate)、吼蟎胺（tebufenpyrad)、唑蟲醯胺 (tolefenpyrad)、畢達本（pyridaben)、畢汰芬 25 320738 200932723 (pyrimidifen)、嘧蟎酯（fluacrypyrim)、依殺蟎 (etoxazole)、芬殺蟎（fenazaquin)、亞醌蜗 (acequinocyl)、合賽多（hexythiazox)、四蜗唤 (clofentezine)、芬柿賜（fenbutatin oxide)、大克蜗 (dicofol)、毆蜗多（propargite)、阿維菌素（abamectin)、 齊蟎素（avermectin)、密滅汀（milbemectin)、三亞蟎 (amitraz)、免速達（be.nsultap)、殺蟲環（thiocyclam)、 _ 硫丹（endosulfan)、季酮蟎酯（spirodiclofen)、表螺曱蜗 酯（spiromesifen)、安伏滅（amidoflumet)及印楝素 (azadirachtin)、溴蜗酯（bromopropylate)、三氯殺蜗礙 (tetradifon)、蟎離丹（chinomethionat)、萘菌素複合物 (polynactin complex)(四活菌素（tetranactin)、二活菌 素（dinactin)及三活菌素（trinactin))、阿維菌素 (abamectin)、氰氟蟲腙（metaflumizon)、氟蟲酿胺 (flubendiamide)、氣蟲苯甲醯胺（chlorantraniliprole) ❹ 及B比福啥左（pyrif luquinazon)。 拒避劑之活性成分之實例包含3, 4-蒈二醇、N，N-二乙 基-間甲苯醯胺、2-(2-羥乙基）-卜哌啶羧酸1-甲基丙基 酯、對薄荷腦-3, 8-二醇及精油，例如海索油（hyssop oi 1)。 增效劑之活性成分之實例包含雙-(2, 3, 3, 3-四氯丙基） 醚（5-421)、^(2-乙基己基）雙環[2.2.1]庚-5-烯-2,3-二 羧醢亞胺（MGK-264)及A-[2-(2-丁氧基乙氧基）乙氧基] -4, 5-亞曱二氧基-2-丙基甲苯（胡椒基丁氧化物 (piperonyl butoxide)) ° 26 320738 200932723 * 藉由下列製備例、調配例及試驗例將更詳細說明本發 明，但本發明並不受限於該等實施例。 首先，敘述本發明化合物之製備例。 製備例1 .在氮環境下，將182毫克1-乙基-3-(3-二曱基胺基丙 基）碳二亞胺鹽酸鹽加入128毫克2, 3, 5, 6-四氟苯甲醇、 128毫克（1R)-順式-3-氰基-2, 2-二甲基環丙烷羧酸、5毫 克4-二曱基胺基吡啶及5毫升（mL)氯仿之混合物中，接著 在室溫攪拌混合物18小時。將反應混合物加入水中，接著 以醋酸乙酯萃取。有機層以無水硫酸鎂脫水，及在減壓下 濃縮。於殘餘物溶於5毫升無水四氫呋喃之溶液中加入 0. 06毫升三乙胺、0. 04毫升醋酸酐及5毫克4-二曱基胺 基吡啶，接著在室溫攪拌混合物18小時以乙醯化剩餘的苯 曱醇。於反應混合物中加入飽和碳酸氫鈉水溶液，且混合 物以醋酸乙酯萃取。有機層以無水硫酸鎂脫水，及濃縮。 φ 所得殘餘物進行矽膠層析術，獲得34毫克下式表示之 (1R)-順式-3-氰基-2, 2-二甲基環丙烧缓酸2, 3, 5，.四氟 苯曱酯： [ C H,C CH,The dose range of the compound is usually 〇〇1 to 1000 mg (mg) per 1 kg (kg) of animal body. The pest control composition of the present invention can be combined with a variety of other insecticides, acaricides, nematicides. Mixtures or combinations of soil pest control agents, fungicides, herbicides, plant growth for 5 weeks, repel lents, synergists, fertilizers and soil conditioners. Examples of active ingredients for insecticides and acaricides include: Organophosphorus compounds such as dichlorvos, fenitrothion, Cyan〇ph〇s, profenofos, Thiifronf (suiprof〇s), phenthoate, isoxathi〇n, tetrachlorvinphos, fenthion, taosson 22 320738 200932723 , (chlorpyrifos), dansson ( Diazinon), acephate, terfufos, phorate, chlorethoxyfos, fosthiazate, ethoprophos, cadusafos, Methidathion, disulfoton, dioxabenzofos, dimethoate, phenathoate, malathion, trichlorphon, valley speed Azinphos-methyl, monocrotophos, ethion, etc.; urethane compounds such as propoxur, carbaryl, beta-indolone (metoxadiazQne) ), Zhong Dingwei (fenobu) Carb), methomyl, thiodicarb, alanycarb, benfuracarb, oxamyl, aldicarb, metimocarb , carbosulfan, ethiofencarb, fenothiocarb, cartap, etc.; pyrethroid compounds, such as allethrin , tralmethrin, pral lethrin, d-phenothrin, d-resmethrin, cyphenothrin, baifenning (permethrin), cypermethrin, alpha-cypermethrin, zeta-cypermethrin, deltamethrin, tralmethrin, savonon ( Cyfluthrin), yS-赛福宁 23 320738 i 200932723 (beta-cyfluthrin), cyhalothrin, lambda-cyhalothrin, d-furamethrin, yipuling (imiprothrin), ethofenprox, fenvalerate, esfenvalerate, Fenpu Ning' (fenpropathrin), silafluofen, bifenthrin, transfluthrin, flucythrinate, tau-f luvalinate, acrinathrin, Tefluthrin, cycloprothrin, metofluthrin, profluthrin, dimefluthrin, empenthrin, fluoride Flumethrin, f luvalinate, 2-mercapto-2-(4-bromodifluorodecyloxyphenyl)propyl (3-phenoxybenzyl)ether and 2, 2, 3, 3-tetradecylcyclopropanecarboxylic acid 5-(2-propynyl)furanmethyl ester; new neonicotinoid compounds, such as acetamiprid, enezapine (nitenpyram), thiacloprid, thiamethoxam, dinotefuran, clothianidine, imidacloprid, etc.; chlorinated hydrocarbon compounds, such as endosulfan (endosu 1 f an ), γ-BHC and 1,1-bis(chlorophenyl)-2, 2, 2-trichloroethanol; phenylnonylphenylurea compounds, for example Lufenuron, chlorfluazuron, hexailumuron, diflubenzuron, triflumuron, defolon 24 320738 200932723 (teflubenzuron), flufenoxuron ), fluazuron, novaluron, triazuron, bistrifluron, flufenoxuron, etc.; juvenile hormone analogues For example, pyriproxyfen, mephiprene, hydroprene, phenoxycarb, etc.; phenyl beta complex compounds, such as pyriprazole, pyridin Pyrafluprole, ethiprole, etc.; benzamidine compounds such as tebufenozide, chromafenozide, methoxyfenozide, chlorfenapyr ( Halofenozide); macrolide compounds, such as polynactin complex (tetranactin, dinactine, and trinactin) Averm (abamectin), avermectin, emamectin benzo benzoate, spinosad, azadirachtin, &gt;milbemectin; and diafenthiuron ), πϋ缉嗣 (pymetrozine), flonicamide, triazamate, buprofezin, spinosad, emamectin benzoate, bromide (chlorphenapyr), indoxacarb MP, pyridalyl, cyromazine, fenpyroximate, tebufenpyrad, tolefenpyrad, Pyripaben, Pidifen 25 320738 200932723 (pyrimidifen), fluacrypyrim, etoxazole, fenazaquin, acequinocyl, hexythiazox , clofentezine, fenbutatin oxide, dicofol, propargite, abamectin, avermectin, milbemectin ), Sanya 螨 (amitraz), speed-free (be .nsultap), thiocyclam, _endosulfan, spirodiclofen, spiromesifen, amidoflumet and azadirachtin, bromine Bromopropylate, tetradifon, chinomethionat, polynactin complex (tetranactin, dinactin, and tripartite) Trinactin, abamectin, metaflumizon, flubendiamide, chlorantraniliprole ❹ and B 福福鲁quinazon ). Examples of the active ingredient of the repellent include 3, 4-decanediol, N,N-diethyl-m-toluidine, 2-(2-hydroxyethyl)-piperidinecarboxylic acid 1-methylpropane Base esters, menthol-3, 8-diol and essential oils such as hysosop oi 1 . Examples of the active ingredient of the synergist include bis-(2,3,3,3-tetrachloropropyl)ether (5-421), ^(2-ethylhexyl)bicyclo[2.2.1]hept-5- Aceene-2,3-dicarboxylimenine (MGK-264) and A-[2-(2-butoxyethoxy)ethoxy]-4, 5-indenylenedioxy-2-propene Toluene (piperonyl butoxide) ° 26 320738 200932723 * The present invention will be explained in more detail by the following Preparation Examples, Formulation Examples and Test Examples, but the present invention is not limited to the Examples. First, a preparation example of the compound of the present invention will be described. Preparation Example 1. 182 mg of 1-ethyl-3-(3-didecylaminopropyl)carbodiimide hydrochloride was added to 128 mg of 2,3,5,6-tetrafluorocarbon under nitrogen atmosphere. a mixture of benzyl alcohol, 128 mg of (1R)-cis-3-cyano-2,2-dimethylcyclopropanecarboxylic acid, 5 mg of 4-didecylaminopyridine and 5 ml of (mL) chloroform. The mixture was then stirred at room temperature for 18 hours. The reaction mixture was added to water and then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. To the solution of the residue in 5 ml of anhydrous tetrahydrofuran, 0. 06 ml of triethylamine, 0. 04 ml of acetic anhydride and 5 mg of 4-didecylaminopyridine, followed by stirring the mixture at room temperature for 18 hours. Remaining phenyl sterol. A saturated aqueous solution of sodium hydrogencarbonate was added and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue obtained by φ was subjected to silica gel chromatography to obtain 34 mg of (1R)-cis-3-cyano-2,2-dimethylcyclopropanone acid 2, 3, 5,. Phenyl phthalate: [ CH, C CH,

(後文中稱為本發明化合物（1))，呈無色液體。 !H-NMR (CDCls, TMS) 5 (ppm) ： 1. 28 (s, 3H), 1. 46 (s, 3H), 27 320738 200932723 1.77 (d, 1H, j = 8.2 Hz), 1.96 (d, iH, J = 8. 2 Hz ), 5. 29 (d, 1H, J = 12. 3 Hz ), 5. 34 (d, iH, J = 12. 3 Hz ), 7. 10-7. 14 (m，1H) 製備例2 除了使用4_甲基-2, 3, 5, 6-四氟苯甲醇取代2, 3, 5, 6一 四氟苯甲醇外，進行如製備例1之相同程序，獲得下式表 示之（1R)-順式—3-氰基-2, 2- —甲基環丙烧竣酸4-甲基 -2，3，5,6 -四氟本甲酉旨..(hereinafter referred to as the compound (1) of the present invention), it is a colorless liquid. !H-NMR (CDCls, TMS) 5 (ppm): 1. 28 (s, 3H), 1. 46 (s, 3H), 27 320738 200932723 1.77 (d, 1H, j = 8.2 Hz), 1.96 (d , iH, J = 8. 2 Hz ), 5. 29 (d, 1H, J = 12. 3 Hz ), 5. 34 (d, iH, J = 12. 3 Hz ), 7. 10-7. 14 (m, 1H) Preparation Example 2 The same procedure as in Preparation Example 1 was carried out except that 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol was used instead of 2,3,5,6-tetrafluorobenzyl alcohol. , (1R)-cis-3-cyano-2,2-methylcyclopropane decanoic acid 4-methyl-2,3,5,6-tetrafluorobenzamide is obtained. .

(後文中稱為本發明化合物（2))，呈無色液體。 !H-NMR (CDCh, TMS) (5 (ppm) : 1. 27 (s, 3H), 1.46 (s, 3H), 1.76 (d, 1H, J = 8. 3 Hz), 1.96 (d, 1H} J = 8. 3 Hz ), 2.29 (t, 3H, J = 2. 1 Hz)，5. 26 (d，1H，j = 12. 2 Hz )， ❹ 5.31 (d, 1H, J = 12.2 Hz ) 製備例3 除了使用4-曱氧基-2,3’5’6-四氟苯甲醇取代2,3, 5, 6-四氟苯曱醇外，進行如製備例1之相同程序，獲得下 式表示之(1R)-順式-3-氰基2-—甲基環丙院魏酸4一甲 氧基-2, 3, 5, 6-四敦苯甲酯：(hereinafter referred to as the compound (2) of the present invention), it is a colorless liquid. !H-NMR (CDCh, TMS) (5 (ppm): 1. 27 (s, 3H), 1.46 (s, 3H), 1.76 (d, 1H, J = 8. 3 Hz), 1.96 (d, 1H } J = 8. 3 Hz ), 2.29 (t, 3H, J = 2. 1 Hz), 5. 26 (d, 1H, j = 12. 2 Hz ), ❹ 5.31 (d, 1H, J = 12.2 Hz) Preparation Example 3 The same procedure as in Preparation Example 1 was carried out except that 4-decyloxy-2,3'5'6-tetrafluorobenzyl alcohol was used instead of 2,3,5,6-tetrafluorobenzophenone. (1R)-cis-3-cyano 2-methylcyclopropene-tertillary acid 4-methoxy-2,3,5,6-tetradendrolyl ester:

320738 28 200932723 (後文中稱為本發明化合物（3))，呈無色液體。 ^-NMR (CDC13, TMS) 5 (ppm) ·· 28(s，3H)，1.46 (s 3H) 1.76 (d，1H，J = 8.3 Hz)，1. 95 (d，1H，j乂 8 3 Hz )， 4. 11 (t，3H，J = 1. 6 Hz)，5.21-5.30 (m，2H ) 製備例4 ’ ❹ 除了使用4-甲氧基曱基~2, 3, 5, 6-四氟笨ψ醇取代 2’3, 5, 6-四氟苯曱醇外，進行如製備例}之相同程序，獲 得下式表示之（1R)-順式-3-氰基-2, 2-二甲基環丙烷羧酸 甲氧基甲基-2, 3, 5, 6-四氟苯甲酯：320738 28 200932723 (hereinafter referred to as the compound (3) of the present invention) is a colorless liquid. ^-NMR (CDC13, TMS) 5 (ppm) ·· 28(s,3H), 1.46 (s 3H) 1.76 (d,1H,J = 8.3 Hz), 1. 95 (d,1H,j乂8 3 Hz ), 4. 11 (t, 3H, J = 1. 6 Hz), 5.21-5.30 (m, 2H ) Preparation 4 ' ❹ In addition to using 4-methoxyindenyl~2, 3, 5, 6- (4R)-cis-3-cyano-2, 2 is obtained by the same procedure as in Preparation Example} except that the tetrafluoroclumol is substituted for 2'3,5,6-tetrafluorobenzophenone. - dimethylcyclopropanecarboxylic acid methoxymethyl-2,3,5,6-tetrafluorobenzyl ester:

(後文中稱為本發明化合物（4))，呈無色液體、 MMR (CDCI3，TMS) (ppm). 1. 28 (s，3H)，1· 46 (s，3H)， 1* 77 (d, 1H, J = 8. 5 Hz), 1. 95 (d, 1H, J = 8. 5 Hz ), ❹ 3. 41 (s，3H)，4. 59 (s，2H)，5· 28 (d，1H，J =i2. 1 Hz)， 5. 34 (d, 1H, J =12. 1 Hz) 製備例5 除了使用4-(2-丙炔基）一2, 3, 5, 6_四氟苯甲醇取代 2, 3, 5, 6-四氟苯曱醇外，進行如製備例1之相同程序.，獲 得下式表示之（1R)-順式氰基_2’ 2_二甲基環丙烷羧酸 4-(2-丙炔基）一2,3,5,6-四氟苯甲酯： 320738 29 200932723(hereinafter referred to as the compound (4) of the present invention), as a colorless liquid, MMR (CDCI3, TMS) (ppm). 1. 28 (s, 3H), 1 · 46 (s, 3H), 1* 77 (d , 1H, J = 8. 5 Hz), 1. 95 (d, 1H, J = 8. 5 Hz ), ❹ 3. 41 (s, 3H), 4. 59 (s, 2H), 5· 28 ( d, 1H, J = i2. 1 Hz), 5. 34 (d, 1H, J = 12. 1 Hz) Preparation Example 5 except that 4-(2-propynyl)-2, 3, 5, 6_ was used. The same procedure as in Preparation Example 1 was carried out except that tetrafluorobenzyl alcohol was substituted for 2,3,5,6-tetrafluorobenzophenone, and (1R)-ciscyano-2'2-dimethyl represented by the following formula was obtained. 4-(2-propynyl)- 2,3,5,6-tetrafluorobenzyl ester of cyclopropanecarboxylic acid: 320738 29 200932723

HsC CH3HsC CH3

(後文中稱為本發明化合物（5))，呈無色液體。 !H-NMR (CDCh, TMS) 5 (ppm) ： 1. 28 (s, 3H), 1.46 (s 3H), 1. 77 (d, 1H, J = 8. 3 Hz), 1. 95 (d, 1H, J = 8. 3 Hz ), 2. 07 (t, 1H, J = 2. 8 Hz), 3. 64-3. 65 (m, 2H) 5 27 (d 1H, J =12.0 Hz), 5.33 (d, 1H, J =12.0 Hz) ®製備例6 除了使用4-甲基硫甲基-2, 3, 5, 6-四氟笨甲醇取代 2, 3, 5, 6-四氰苯甲醇外，進行如製備例丨之相同程序，獲 得下式表示之（1R)-順式-3-氰基-2, 2-二甲基環丙烧緩酸 4-曱基硫甲基-2,3,5,6-四氟苯甲酯：(hereinafter referred to as the compound (5) of the present invention), it is a colorless liquid. !H-NMR (CDCh, TMS) 5 (ppm): 1. 28 (s, 3H), 1.46 (s 3H), 1. 77 (d, 1H, J = 8. 3 Hz), 1. 95 (d , 1H, J = 8. 3 Hz ), 2. 07 (t, 1H, J = 2. 8 Hz), 3. 64-3. 65 (m, 2H) 5 27 (d 1H, J =12.0 Hz) , 5.33 (d, 1H, J = 12.0 Hz) ®Preparation Example 6 In addition to using 4-methylthiomethyl-2,3,5,6-tetrafluorobenzol to replace 2,3,5,6-tetracyanobenzene Except for methanol, the same procedure as in Preparation Example was carried out to obtain (1R)-cis-3-cyano-2,2-dimethylcyclopropanone acid 4-mercaptothiomethyl-2 ,3,5,6-tetrafluorobenzyl ester:

(後文中稱為本發明化合物（6))，呈無色液體。 ^-NMR (CDCh, TMS) (5 (ppm) ： 1. 28 (s, 3H), 1.46 (s, 3H), 1.77 (d，1H，J = 8. 2 Hz), 1. 96 (d，1H，J = 8.2 Hz), 2. 13 (t，3H, J = 1.0 Hz), 3. 78 (t, 2H，J = i.o Hz) 5-26-5.35 (m, 2H) 製備例7 ' 降了使用4-(2-丙烯基）-2, 3, 5, 6-四氟苯甲醇取代 2’3, 5, 6-四氟苯甲醇外，進行如製備例i之相同程序，獲 320738 30 200932723 得下式表不之（1R)_順式_3-氮基-2,2-二甲基環丙烧幾酸 4-(2-丙婦基）-2，3，5,6-四氟j苯甲酯：(hereinafter referred to as the compound (6) of the present invention), it is a colorless liquid. ^-NMR (CDCh, TMS) (5 (ppm): 1. 28 (s, 3H), 1.46 (s, 3H), 1.77 (d, 1H, J = 8. 2 Hz), 1. 96 (d, 1H, J = 8.2 Hz), 2. 13 (t, 3H, J = 1.0 Hz), 3. 78 (t, 2H, J = io Hz) 5-26-5.35 (m, 2H) Preparation 7 ' Drop The same procedure as in Preparation Example i was carried out except that 4-(2-propenyl)-2,3,5,6-tetrafluorobenzyl alcohol was substituted for 2'3,5,6-tetrafluorobenzyl alcohol to obtain 320738 30 200932723 The following formula (1R)_cis_3-nitro-2,2-dimethylcyclopropanoic acid 4-(2-propanyl)-2,3,5,6-four Fluorine x benzyl ester:

(後文中稱為本發明化合物（7))，呈無色液體。 ^-NMR (CDC13, TMS) (5 (ppm) ： 1.28 (s, 3H), 1.46 (s, 3H), 1.77 (d, 1H, J = 8. 3 Hz), 1.96 (d, 1H, J = 8. 3 φ Hz), 3.47-3.50 (m, 2H), 5. 08-5. 13 (m, 2H), 5.25-5.33 (m, 2H), 5.84-5. 94 (m, 1H) 製備例8 除了使用2,3,4,5,6-五氟苯甲醇取代2,3,5,6-四氟 苯曱醇外，進行如製備例1之相同程序，獲得下式表示之 (1R)-順式-3-氰基-2，2-二曱基環丙院叛酸2, 3, 4, 5，6-五 氟苯曱酯： 一 — u r&gt;(hereinafter referred to as the compound (7) of the present invention), it is a colorless liquid. ^-NMR (CDC13, TMS) (5 (ppm): 1.28 (s, 3H), 1.46 (s, 3H), 1.77 (d, 1H, J = 8. 3 Hz), 1.96 (d, 1H, J = 8. 3 φ Hz), 3.47-3.50 (m, 2H), 5. 08-5. 13 (m, 2H), 5.25-5.33 (m, 2H), 5.84-5. 94 (m, 1H) Preparation 8 The same procedure as in Preparation Example 1 was carried out except that 2,3,4,5,6-pentafluorobenzyl alcohol was used in place of 2,3,5,6-tetrafluorobenzophenone, and (1R) was obtained. -cis-3-cyano-2,2-dimercaptocyclopropene rebel 2,3,4,5,6-pentafluorobenzoate: a-u r&gt;

(後文中稱為本發明化合物（8))。 接著，以參考製備例敘述用於製造本發明化合物之中 間物之製備。 參考製備例1(hereinafter referred to as the compound (8) of the present invention). Next, the preparation for the intermediate of the compound of the present invention will be described with reference to the preparation examples. Reference preparation example 1

31 320738 200932723 於含有20.2克（g)(lS)-順式-2, 2-二甲基-3-(2-曱基 丙烯基）環丙烷羧酸之120毫升四氫呋喃[THF]溶液中加入 12.8克三乙胺。在0°C於混合物中滴加16.8克草醯氣，接 著在室溫攪拌12小時。然後，將反應混合物倒進40克28% 氨水，接著在室溫攪拌2小時。反應混合物以醋酸乙酯萃 取，且有機層依次以水及飽和鹽水洗蘇。有機層以無水硫 酸鎂脫水，及在減塵下濃縮，獲得17. 5克（1S)-順式-2, 2-二曱基-3-(2-曱基丙烯基）環丙烷曱醯胺，呈無色結晶。 ^-NMR (CDCls) (5(ppm)：1.20 (s, 3H), 1.24(s, 3H&gt;, 1.47 (d, 1H，J = 8.5 Hz)，1.72 (d，3H，J = 1.2 Hz), 1.74 (d, 1H, J = 8.5Hz), 1.77 (s, 3H), 5.35-5.38 (m, 1H), 5.57 (brs, 2H) 參考製備例2 u r' γμ_ι I ^ .31 320738 200932723 Add 12.8 g of a solution containing 20.2 g of (lS)-cis-2,2-dimethyl-3-(2-mercaptopropenyl)cyclopropanecarboxylic acid in 120 ml of tetrahydrofuran [THF]. Triethylamine. 16.8 g of grass cockroach was added dropwise to the mixture at 0 ° C, followed by stirring at room temperature for 12 hours. Then, the reaction mixture was poured into 40 g of 28% aqueous ammonia, followed by stirring at room temperature for 2 hours. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed sequentially with water and saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced dust to give 17.5 g of (1S)-cis-2,2-dimercapto-3-(2-mercaptopropenyl)cyclopropanoguanamine. It is colorless crystal. ^-NMR (CDCls) (5 (ppm): 1.20 (s, 3H), 1.24 (s, 3H&gt;, 1.47 (d, 1H, J = 8.5 Hz), 1.72 (d, 3H, J = 1.2 Hz), 1.74 (d, 1H, J = 8.5 Hz), 1.77 (s, 3H), 5.35-5.38 (m, 1H), 5.57 (brs, 2H) Reference Preparation 2 ur' γμ_ι I ^ .

於11. 9.克（IS)-順式-2，2-二曱基-3-(2 -甲基丙稀基) 環丙烷甲醯胺中加入18.9毫升醋酸酐，接著在室溫攪拌 30分鐘，及進一步在120°C攪拌3. 5小時。將反應混合物 倒進150毫升冰水及120毫升醋酸乙酯之混合物中，接著 攪拌1小時。然後，將有機層分離，且水層進一步以醋酸 乙酯萃取。將所得有機層合併，及依次以水、飽和碳酸氳 鈉水溶液及飽和鹽水洗滌。有機層以無水硫酸鎂脫水，及 在減壓下濃縮。所得殘餘物進行矽膠層析術，獲得7. 02克 32 320738 200932723 (IS)-順式-2, 2-二曱基-3-(2-曱基丙稀基）環丙烧甲腈’呈 淡黃色液體。 'H-NMR (CDCla) ^ (ppm) ： 1. 19 (s, 3H), 1.20 (s, 3H), 1.45 (d, 1H, J = 8. 5 Hz ), 1. 73 (s, 3H), 1. 79 (s, 3H), 1. 81 (d, 1H, J = 8.5 Hz ), 5.01-5.03 (m, 1H) 參考製備例3Add 11.89 ml of acetic anhydride to 11.9 g of (IS)-cis-2,2-dimercapto-3-(2-methylpropenyl)cyclopropanecarbamide, followed by stirring at room temperature 30 5小时。 The minute, and further stirred at 120 ° C for 3.5 hours. The reaction mixture was poured into a mixture of 150 ml of ice water and 120 ml of ethyl acetate, followed by stirring for 1 hour. Then, the organic layer was separated, and the aqueous layer was further extracted with ethyl acetate. The obtained organic layers were combined and washed successively with water, a saturated aqueous solution of sodium carbonate and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 7.02 g of 32 320738 200932723 (IS)-cis-2,2-dimercapto-3-(2-mercaptopropyl)cyclopropanone carbonitrile. Light yellow liquid. 'H-NMR (CDCla) ^ (ppm): 1. 19 (s, 3H), 1.20 (s, 3H), 1.45 (d, 1H, J = 8. 5 Hz ), 1. 73 (s, 3H) , 1. 79 (s, 3H), 1. 81 (d, 1H, J = 8.5 Hz ), 5.01-5.03 (m, 1H) Reference Preparation Example 3

於50毫升第三丁醇及130毫升水之混合物中加入1· 23 克（IS)-順式-2, 2-二甲基-3-(2-曱基丙烯基）環丙烷甲 腈，及於其内進一步加入13. 0克偏過碘酸鈉及210毫克過 錳酸鉀’接著在室溫攪拌5天。反應混合物在減壓下濃縮， 蒸餾除去第三丁醇，且所得水溶液以醋酸乙酯萃取。於有 機層中加入5%碳嫂鉀水溶液，接著攪拌及進一步分層。於 ❹所得水層中加入5%鹽酸以將pH值調整為3,且該水層以醋 酸乙醋.萃取。所得有機層以無水硫酸鎂脫水，及在減壓下 濃縮，獲得0.69克（1R)-順式_3_氰基_2,2_二曱基環丙烷 羧酸，呈無色液體。 !H-NMR CCDCls) &lt;5 (ppm) ： 1. 3l (Sj 3H), 1. 48 (s, 3H), 1. 62 (brs, 1H), 1.80 (d, 1H, J = g. 5 Hz) 1.99 (d, 1H, J = 8. 5 Hz) 經本發明方法之本發明化合物之製備例將在後文中描 述。 320738 33 200932723 製備例9 (歩驟1) 於50毫升第三丁醇及130毫升水之混合物中加入123 克（1S)-順式-2, 2-二甲基-3-(2-甲基丙埽基）環丙燒甲 腈’及於其内進一步加入13. 0克偏過蛾酸鈉及21〇毫克過 錳酸鉀，接著在室溫攪拌5天。反應混合物在減壓下濃縮， 蒸餾除去第三丁醇，且所得水溶液以醋酸乙酯萃取。於有 ❹機層加入5%碳酸钟水溶液’接著擾拌並進一步分離。於所 得水層中加入5%鹽酸以將PH值調整為3’且該水層以醋酸 乙酯萃取。所得有機層以無水硫酸鎂脫水，及在減壓下濃 縮，獲得0· 69克（1R)-順式-3-氰基-2, 2-二甲基環丙烷羧 酸。.. (步驟2) 在氮環境下’將182毫克1-乙基-3-(3-二甲基胺基丙 基）碳二亞胺鹽酸鹽加入128毫克步驟1所製得之（1幻_順 Θ 式_3一氰基-2, 2-二甲基環丙烷羧酸、128毫克2, 3, 5, 6-四 氟苯曱醇、5毫克4-二曱基胺基η比啶及5毫升氯仿之混合 物中’接者在室溫授拌18小時。將反應混合物加入水中， 及以醋酸乙酯萃取。有機層以無水硫酸鎂脫水，及在減壓 下濃縮。於含有殘餘物之5毫升無水四氫呋喃溶液中加入 〇· 04毫升醋酸酐及5毫克4-二甲基胺基吡啶，且所得混合 物在室溫攪拌18小時以乙醯化剩餘的苯甲醇《於反應混合 物中加入飽和碳酸氫鈉水溶液，且混合物以醋酸乙酯萃 取。有機層以無水硫酸鎂脫水，及濃縮。所得殘餘物進行 34 320738 200932723 碡 矽膠層析術，獲得34毫克（1R)-順式-3-氰基_2,2〜二 環丙烧羧酸2, 3, 5, 6-四氟苯曱酯。 後文將敘述調配例。所有a份〃係指重量份。 調配例1 將20份本發明化合物（1)至（8)中之任一者溶於65份 二曱苯’於其内加入15份Sorpol 3005X(東邦化學工業公 司（Toh〇 Chemical Co.，Ltd·)之註冊商標），混合物經攪 0 拌以徹底混合，獲得可乳化濃縮物。 調配例2 將5份Sorpol 3005X添加至40份本發明化合物q) 至（8) t之任一者，將混合物徹底混合，於其内加入32份Adding 23.23 g of (IS)-cis-2,2-dimethyl-3-(2-mercaptopropenyl)cyclopropanecarbonitrile to a mixture of 50 ml of tert-butanol and 130 ml of water, and Further, 13.0 g of sodium metaperiodate and 210 mg of potassium permanganate were further added thereto, followed by stirring at room temperature for 5 days. The reaction mixture was concentrated under reduced pressure, and then evaporated to ethyl ether. A 5% aqueous solution of potassium cesium carbonate was added to the organic layer, followed by stirring and further stratification. To the aqueous layer obtained from hydrazine, 5% hydrochloric acid was added to adjust the pH to 3, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give &lt;RTI ID=0.0&gt;&gt; !H-NMR CCDCls) &lt;5 (ppm): 1. 3l (Sj 3H), 1. 48 (s, 3H), 1. 62 (brs, 1H), 1.80 (d, 1H, J = g. 5 Hz) 1.99 (d, 1H, J = 8. 5 Hz) The preparation of the compound of the present invention by the method of the present invention will be described later. 320738 33 200932723 Preparation 9 (Scheme 1) 123 g of (1S)-cis-2,2-dimethyl-3-(2-methyl) was added to a mixture of 50 ml of tributanol and 130 ml of water. Further, 1 g of sodium molybdate and 21 mg of potassium permanganate were further added thereto, followed by stirring at room temperature for 5 days. The reaction mixture was concentrated under reduced pressure, and then evaporated to ethyl ether. A 5% aqueous solution of carbonic acid was added to the buffer layer' followed by scramble and further separation. 5% hydrochloric acid was added to the obtained aqueous layer to adjust the pH to 3' and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give &lt;RTIgt;&lt;/RTI&gt; .. (Step 2) Add 182 mg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride to 128 mg of step 1 under nitrogen atmosphere (1)幻_顺Θ _3-cyano-2,2-dimethylcyclopropanecarboxylic acid, 128 mg of 2,3,5,6-tetrafluorobenzofuran, 5 mg of 4-didecylamino η In a mixture of pyridine and 5 ml of chloroform, the mixture was stirred at room temperature for 18 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. To a solution of 5 ml of anhydrous tetrahydrofuran, 〇·04 ml of acetic anhydride and 5 mg of 4-dimethylaminopyridine were added, and the resulting mixture was stirred at room temperature for 18 hours to acetify the remaining benzyl alcohol. Saturated aqueous sodium hydrogencarbonate solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated. The obtained residue was subjected to hexanes chromatography, to give 34 mg (1R)-cis-3- Cyano 2,2~dicyclopropanecarboxylic acid 2,3,5,6-tetrafluorobenzoate. The formulation examples will be described later. Parts by weight. Formulation Example 1 20 parts of the present compounds (1) to (8) were dissolved in 65 parts of diphenylbenzene, and 15 parts of Sorpol 3005X (Toh Chemical Co., Ltd.) was added thereto. ., Ltd.), the mixture is thoroughly mixed with 0 to obtain an emulsifiable concentrate. Formulation Example 2 5 parts of Sorpol 3005X is added to 40 parts of any of the compounds of the present invention q) to (8) t Mix the mixture thoroughly and add 32 parts to it.

Carplex #80 (Sionogi Pharmaceutical Co.，Ltd.之註冊 商標’為合成性水合氧化矽）及23份300篩目之石夕藻土， 並將混合物以果汁機擾拌而混合，獲得可濕性粉劑。 調配例3 © 在混合1.5份本發明化合物（1)至（8)中之任一者、1 份Tokuseal GUN (合成性水合氧化碎，德山公司（Tokuyama Corp.)製造）、2份Reax 85A (木質素確酸納’維實偉克化 學公司（West Vaco Chemicals)製造）、30 份 Bentonite Fuji (膨潤土，禾菌公司（Ho jun Corp.)製造）及65. 5份Shokozan A黏土（高嶺土黏土，Shokozan Kogyosho製造）後’將經混 合之組份徹底地研磨，並於其内加入水。混*合物經徹底揉 合，以擠壓製粒機製粒’再經乾燥，獲得1. 5%粒劑。 調配例4 ' 35 320738 200932723 、， 1 在混合丨〇份本發明化合物（1)至（8)中之任一者、10 份苯基二甲苯基乙烧及0. 5ι份Sumi jul L-75 (甲苯二異氮 酸醋（tolylene diisocyanate)，住友拜耳聚胺g旨公司 (Sumitomo Bayer Urethane Ltd.)製造）後，將混合物加入 20份10%阿拉伯膠水溶液中’接著以均質機擾摔，獲得且 有平均粒徑20微米（/zm)之乳液。該乳液進一步與2份乙 二醇混合’且混合物在60°C於溫水浴中攪拌24小時，獲 ❹得微膠囊漿料。另外’將〇· 2份二仙膠（xanthan gum)及 1. 0份Veegurn'R (梦酸銘鎮’二洋化成公司（Sanyo Chemical) 製造）分散於56. 3份離子交換水’製得增稠劑溶液。將42. 5 份微膠囊漿料及57· 5份增稍劑溶液混合，獲得微膠囊調配 物。 調配例5 在混合10份本發明化合物（1)至（8)中之任一者及10 份苯基二曱苯基乙烷後，將混合物加入2〇份1〇%聚乙二醇 ❹水溶液中，接著以均質機攪拌’獲得具有平均粒徑3微米 之乳液。另外，將0. 2份三仙膠及1. 0份Veegum R (矽酸 銘鎮，三洋化成公司製造）分散於58.8份離子交換水，製 得增稠劑溶液。將40份乳液及6〇份增稠劑溶液混合，獲 得可流動性調配物。 調配例6 將5份本發明化合物（1)至（8)中之任一者、3份 Carpi ex #80 (合成性水合氧化梦 ’ Sionogi Pharmaceutical Co.，Ltd.之註冊商標）、Ο.3份pAP(磷酸一異丙酯及磷酸 36 320738 200932723 二異丙酯之混合物）及91· 7份滑石（3〇〇篩目）以果汁機授 拌而混合，獲得粉劑。 調配例7 將0· 1份本發明化合物（1)至（8)中之任一者溶於1〇^ 二氯曱烷，並於其内加入8 9. 9份脫臭煤油，獲得油性溶液^ 調配例8 胃.. ❹ ❹ 將1份本發明化合物（1)至（8)中之任一者、5# 甲烧及34份脫臭煤油混合及溶解，填充所得溶液至 容器中’加裝閥門至該容器’再於減壓下透過該閱門 60份推進劑（液化石油氣)至容器中，獲得油性氣霧劑。充 調配例9 ° 將0.6份本發明化合物（1)至（8)中之杠—土 ^ 任一者、5份- 甲苯、3. 4份脫臭煤油及1份山梨醇軒單月杆酸酉t (sorbitan monolaurateXLeodoi SP、Ll〇，&amp;王I 司〔 (：〇_，1^(1.)製造，111^8.6)混合及溶解，1、&amp;0 50份水至氣霧劑容器中，加裝閥門至該容器，所合液及 透過該閥門填充40份推進劑（液化石油翁、再於減壓下 米u至容器中，媒埋 水性氣霧劑。 調配例10 將0. 3克本發明化合物（1)至（8)中之任—々 升丙酮，均勻地混合溶液與99.7克壎香 溶於20毫 於其 模製及乾燥該混 4 : 3 : 3之燻香材料粉末、酒糟粉及木粉之^$比例為 内加入100毫升水，徹底地揉合混合物，σ ， 合物’獲得殺蟲燒香劑 320738 37 200932723 調配例11 將0.8克本發明化合物（1)至（8)中之任一者及0.4克 胡椒基丁氧化物溶於丙酮，調整總體積至10毫升，再將 0. 5毫升該溶液均勻地含浸於2. 5公分（cm)xl. 5公分且0. 3 ~ 公分厚之電殺蟲片的基料（呈平板狀，經由硬化棉絨與紙漿 _ 所構成之纖維而製得），獲得電殺蟲片。 調配例12 義 將3份本發明化合物（1)至（8)中之任一者溶於97份脫 〇 臭煤油，該溶液置於氯乙烯製成之容器中，於該容器中插 入其上半部可經由加熱器加熱之液體吸收芯（經由利用黏 結劑使無機粉末硬固，接著再經燒結而製得），獲得液體吸 收芯型熱散發式裝置之組件。 調配例13 將100毫克本發明化合物之任一者溶於適當量之丙 酮，並含浸於4. 0公分x4. 0公分及厚度1. 2公分之多孔陶 © 瓷板片，獲得熱燻蒸劑。 調配例14 將100微克（//g)本發明化合物（1)至（8)中之任一者 溶於適當量之丙酮，均勻地將該溶液塗在2公分x2公分且 厚度0.3毫米（mm)之濾紙上，並風乾以除去丙酮，獲得室 溫揮發性調配物。 後文將敘述試驗例，其係顯示以本發明化合物作為害 蟲防治組成物之活性成分時的有效性。 本發明化合物（1)至（6)係作為試驗例1中之試驗化合 38 320738 i 200932723 物’而本發明化合物（7)係用於試驗例2中。 試驗例中，亦夜用下列化合物作為比較着 JP 05-32509 A所述之（1R)-反式-3-(2、甲^照化合物： -2,2-二甲基環丙炫羧酸2,3,5,6-四氟苯甲酽1丙歸基） 為比較化合物Q)， 後文中稱 JP 11-222463 A所述之（1R)-反式-3-(2、甲基〜 -2, 2-二甲基環丙烷羧酸4-曱氧基-2, 3, 5, 两埽基） ❹後文中稱為比較化合物（B)， 本甲酯， JP 2001-11022 a 戶斤述之（1R)-反式-3-（2-甲基 1 〜2,2-二甲基環丙烷羧酸4-甲氧基甲基-2,3 5 丙烯基） ，〜3,卜四氟裳 酯，後文中稱為比較化合物（C)， Τ JP 61-207361 A所述之（1R)_反式-3-(2~甲基一卜丙烯美 、2, 2-二甲基環丙烷羧酸4-(2-丙炔基）-2^ 5,6一四氣^甲&gt; 酯，後文中稱為比較化合物（D)， JP 57-123146 A 所述之（1R)-反式-Z-3-(2-氯-3,3 3-=- .甲基-丙婦基）一2，2 -一曱基壤丙燒叛酸4-甲基硫甲其 ~2’ 3, 5, 6-四氟苯甲酯’後文中稱為比較化合物（E)，及Carplex #80 (Sionogi Pharmaceutical Co., Ltd.'s registered trademark 'is synthetic hydrated cerium oxide) and 23 parts of 300 mesh of Shishizao soil, and the mixture is mixed with a juice machine to obtain a wettable powder. . Formulation Example 3 © Mixing 1.5 parts of any of the present compounds (1) to (8), 1 part of Tokuseal GUN (synthetic hydrated oxidized granule, manufactured by Tokuyama Corp.), and 2 parts of Reax 85A (Lignin sulphate, manufactured by West Vaco Chemicals), 30 parts of Bentonite Fuji (bentonite, manufactured by Ho jun Corp.) and 65. 5 parts of Shokozan A clay (kaolin clay) After the manufacturing of Shokozan Kogyosho), the mixed components were thoroughly ground and water was added thereto. The 5% granules were obtained by the granules of the granules. 5份份 Sumi jul L-75 (Tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Ltd.), the mixture was added to 20 parts of 10% aqueous gum arabic solution, and then it was smashed by a homogenizer. And there is an emulsion having an average particle diameter of 20 μm (/zm). The emulsion was further mixed with 2 parts of ethylene glycol' and the mixture was stirred at 60 ° C for 24 hours in a warm water bath to obtain a microcapsule slurry. In addition, '2 parts of xanthan gum and 1.0 part of Veegurn'R (made by Sanyo Chemical Co., Ltd.) were dispersed in 56.3 parts of ion-exchanged water'. Thickener solution. 42.5 parts of the microcapsule slurry and 57.5 parts of the enhancer solution were mixed to obtain a microcapsule formulation. Formulation Example 5 After mixing 10 parts of any of the present compounds (1) to (8) and 10 parts of phenyldiphenylene phenylethane, the mixture was added to 2 parts of a 1% by weight aqueous solution of polyethylene glycol hydrazine. Then, an emulsion having an average particle diameter of 3 μm was obtained by stirring with a homogenizer. Further, 0.2 part of Sanxian gum and 1.0 part of Veegum R (manufactured by Sanyo Chemical Co., Ltd.) were dispersed in 58.8 parts of ion-exchanged water to prepare a thickener solution. 40 parts of the emulsion and 6 parts of the thickener solution were mixed to obtain a flowable formulation. Formulation Example 6 5 parts of any one of the present compounds (1) to (8), 3 parts of Carpi ex #80 (registered trademark of Sionogi Pharmaceutical Co., Ltd.), Ο.3 A portion of pAP (monoisopropyl phosphate and phosphoric acid 36 320738 200932723 diisopropyl ester) and 91. 7 parts of talc (3 mesh mesh) were mixed by a juice machine to obtain a powder. Formulation Example 7 0.1 part of any one of the present compounds (1) to (8) is dissolved in 1 〇 dichloro decane, and 89.9 parts of deodorized kerosene is added thereto to obtain an oily solution. ^ Preparation Example 8 Stomach: ❹ ❹ 1 part of the present compound (1) to (8), 5# toxin and 34 parts of deodorized kerosene are mixed and dissolved, and the resulting solution is filled into a container. A valve is placed in the container and then 60 parts of propellant (liquefied petroleum gas) is passed through the reading door to the container under reduced pressure to obtain an oily aerosol. Charged Formulation 9 ° 0.6 part of the compound of the present invention (1) to (8) in the bar - soil ^ any, 5 parts - toluene, 3.4 parts of deodorized kerosene and 1 part of sorbitol porphyrin酉t (sorbitan monolaurateXLeodoi SP, Ll〇, &amp; Wang I Division [(:〇_,1^(1.), 111^8.6) mixed and dissolved, 1, &amp; 0 50 parts water to aerosol container Adding a valve to the container, filling the liquid and filling the propellant through the valve (liquefied petroleum oil, and then decompressing the rice into the container, embedding the aqueous aerosol. The mixing example 10 will be 0. 3 g of any one of the present compounds (1) to (8) - acetone is added, the solution is uniformly mixed with 99.7 g of musk dissolved in 20 ml of the moulding and drying of the blended 4:3:3 incense material Powder, distiller's powder and wood powder are added to 100 ml of water, thoroughly blending the mixture, σ, compound 'obtains insecticidal scenting agent 320738 37 200932723 Formulation Example 11 0.8 g of the present compound (1) 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 (cm) xl. 5 cm and 0. 3 ~ cm thick electric insecticide tablet base (made in the form of a flat plate, made of hardened lint and pulp _ fibers) to obtain electric insecticidal tablets. Example 12 3 parts of the present compound (1) to (8) were dissolved in 97 parts of deodorized kerosene, and the solution was placed in a container made of vinyl chloride, and the upper half was inserted into the container. The liquid absorption core (which can be obtained by hardening the inorganic powder by using a binder, followed by sintering) to obtain a component of the liquid absorption core type heat dissipation device. Formulation Example 13 100 mg of the present invention Any one of the compounds is dissolved in an appropriate amount of acetone and impregnated with 4. 0 cm x 4. 0 cm and a thickness of 1.2 cm of porous ceramics © porcelain sheets to obtain a hot fumigant. Formulation Example 14 100 μg (/ /g) Any one of the present compounds (1) to (8) is dissolved in an appropriate amount of acetone, and the solution is uniformly applied to a filter paper of 2 cm x 2 cm and a thickness of 0.3 mm (mm), and air-dried to The acetone is removed to obtain a room temperature volatile formulation. The test examples will be described later, which are shown in The effectiveness of the compound of the invention as an active ingredient of a pest control composition. The compounds (1) to (6) of the present invention are used as test compound 38 320738 i 200932723 in Test Example 1 and the compound (7) of the present invention is used. In Test Example 2. In the test example, the following compounds were also used as the (1R)-trans-3-(2, 2-methyl compound: -2,2-dimethyl group as described in JP 05-32509 A. Cyclopropanecarboxylic acid 2,3,5,6-tetrafluorobenzhydryl 1 propyl group) For comparison of compound Q), it is referred to as (1R)-trans-3-(JP) described in JP 11-222463 A. 2. Methyl~-2,2-dimethylcyclopropanecarboxylic acid 4-decyloxy-2,3,5, bis-indenyl) hereinafter referred to as comparative compound (B), methyl ester, JP 2001 -11022 a (1R)-trans-3-(2-methyl-1~2,2-dimethylcyclopropanecarboxylic acid 4-methoxymethyl-2,3 5 propenyl), ～3,Butetrafluoroacetate, hereinafter referred to as Comparative Compound (C), ( JP 61-207361 A (1R)_trans-3-(2~methyl-di-propene, 2, 2 4-(4-propynyl)-2^5,6-tetrahydro-methyl ester of dimethylcyclopropanecarboxylic acid, hereinafter referred to as comparative compound (D), JP 57-123146 A (1R)-trans-Z-3-(2-chloro-3,3 3-=-.methyl-propylglycosyl)- 2,2-one-based Acid 4-methylthiomethan~2' 3, 5, 6-tetrafluorobenzyl ester 'hereinafter referred to as comparative compound (E), and

Pestic· Sci· 1976. 7，492-498 所述之（1R)-反式-3-(2- 甲基-l-丙烯基）-2,2-二甲基環丙烷羧酸5-苯甲基呋喃-3_ 基甲酯，後文中稱為比較化合物（X)。 試驗例1 將0.025份試驗化合物溶於1〇份二氯甲烷，並將該溶 液與89. 975份脫臭煤油混合，製得〇. 025%油性溶液。 釋放10隻德國蜚蠊（幻aiteJJa ^nHa/jica)(分別為5 320738 39 200932723Pestic·Sci· 1976. 7,492-498 (1R)-trans-3-(2-methyl-l-propenyl)-2,2-dimethylcyclopropanecarboxylic acid 5-benzyl The phenylfuran-3-yl methyl ester, hereinafter referred to as the comparative compound (X). Test Example 1 0.025 parts of the test compound was dissolved in 1 part of dichloromethane, and the solution was mixed with 89.975 parts of deodorized kerosene to prepare a 02.5% oily solution. Release 10 German cockroaches (phantom aiteJJa ^nHa/jica) (5 320738 39 200932723 respectively

I 隻雄性及5隻雌性）到内壁中塗有奶油的試驗容器（直徑 8.75公分，高度7.5公分，在底部有16篩目之線網）中。 將該容器置於試驗箱（底部：46公分\46公分，高度：70 公分）之底部。從高於該容器上表面之60公分處，以噴槍 (霧化壓力0.4 kg/cm2)喷佈1.5毫升上述製得之油性製 劑。一個容器係以一種油性溶液喷佈。噴佈後30秒，將容 器自試驗箱取出。靜置一段特定時間後（2分鐘後），計算 ^ 被擊倒的昆蟲數（二重複之平均值）。結果係顯示於表1中。 〇 表1 試驗化合物 2分鐘後被擊倒的昆蟲數 本發明化合物（1) 7 本發明化合物（2) 7 本發明化合物（3) , 9 本發明化合物(4) 10 本發明化合物（5) 10 本發明化合物（6) 10 比較化合物（A) 0 比較化合物（B) 0 比較化合物（C) 2 比較化合物（D) 4 比較化合物（E) 0 比較化合物（X) 0 40 320738 200932723 試驗例2 將試驗化合物溶於比率為9 : 1之異烷烴有機溶劑 (Isopar Μ，艾克森石油公司（Exxon)製造）及二氯曱烧之混 合溶劑中，以製備0. 025%油性溶液。 釋放20隻普通家蠅（M/sca do/nesfca)到各邊為70公 分之立方箱。從該箱之侧壁的小窗；利用喷槍以88xl04Pa 的壓力將0.7毫升所製‘得之油性溶液噴佈到該箱内。然 後，一段特定時間後（5分鐘後），計算被擊倒的昆蟲數(二 重複之平均值）。結果係顯示於表2中。 表2 5分鐘後被擊倒的昆蟲數 本發明化合物（7) 20 比較化合物（X) 2 產業利用性 〇 由於本發明化合物具有優異的害蟲防治效果，因此該 化合物係適用於作為害蟲防治組成物之活性成分。 【圖式簡單說明】 無。 【主要元件符號說明】 〇 '、、、 41 320738I male and 5 female) to the inner wall coated with a cream test container (8.55 cm in diameter, 7.5 cm in height, 16 mesh mesh at the bottom). Place the container at the bottom of the test chamber (bottom: 46 cm / 46 cm, height: 70 cm). From the 60 cm above the upper surface of the container, 1.5 ml of the above-prepared oily preparation was sprayed with a spray gun (atomization pressure of 0.4 kg/cm2). A container is sprayed with an oily solution. The container was taken out of the test chamber 30 seconds after the spray. After standing for a specific period of time (after 2 minutes), calculate the number of insects knocked down (average of the two replicates). The results are shown in Table 1. 〇 Table 1 Number of insects which were knocked down after 2 minutes of the test compound Compound (1) 7 The compound of the present invention (2) 7 The compound of the present invention (3), 9 The compound of the present invention (4) 10 The compound of the present invention (5) 10 The present compound (6) 10 Comparative compound (A) 0 Comparative compound (B) 0 Comparative compound (C) 2 Comparative compound (D) 4 Comparative compound (E) 0 Comparative compound (X) 0 40 320738 200932723 Test example 2 025%油性溶液。 The test compound was dissolved in a ratio of 9: 1 isoparaffin organic solvent (Isopar Μ, manufactured by Exxon) (Exxon) and a mixture of dichlorohydrazine to prepare a 0. 025% oily solution. Release 20 common houseflies (M/sca do/nesfca) to 70 cm cubes on each side. A small window from the side wall of the box; a spray gun was used to spray 0.7 ml of the prepared oily solution into the tank at a pressure of 88 x 104 Pa. Then, after a certain period of time (after 5 minutes), count the number of insects knocked down (average of the two replicates). The results are shown in Table 2. Table 2 Number of insects knocked down after 5 minutes Compound (7) 20 Comparative compound (X) 2 Industrial utilization 〇 Since the compound of the present invention has an excellent pest control effect, the compound is suitable for use as a pest control composition. Active ingredient. [Simple description of the diagram] None. [Main component symbol description] 〇 ', ,, 41 320738

Claims (1)

200932723 七、申請專利範圍： 1. 一種式（1)之環丙烷羧酸酯：200932723 VII. Patent application scope: 1. A cyclopropane carboxylate of formula (1): ψ (1) 式中，R1表示氳原子、氟原子、a-C4烧基、C2-C4烯 基、C2-C4炔基、C1-C4烷氧基、（(：1艽4烷基）氧基曱 基或（C1-C4烷基）硫甲基。 〇 2. 如申請專利範圍第1項之環丙烷羧酸酯，其中，R1為氫 原子、氟原子、曱基、2-丙烯基、2-丙炔基、甲氧基、 曱氧基甲基或曱基硫甲基。 3. —種害蟲防治組成物，包括如申請專利範圍第1或2 項之環丙烷羧酸酯作為活性成分。 4. 一種害蟲防治方法，包括對害蟲或該害蟲棲息地施用有 效量之如申請專利範圍第1或2項之環丙烷羧酸酯。 5. —種用於製造如申請專利範圍第1或2項之環丙烷羧酸 酯之方法，其包括下列步驟： 在锰或釕之氧化物的存在中，使式（6)之化合物：ψ (1) wherein R1 represents a halogen atom, a fluorine atom, an a-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, or a ((:1艽4 alkyl)oxy group. A cyclopropanecarboxylate of the formula (1), wherein R1 is a hydrogen atom, a fluorine atom, a fluorenyl group, a 2-propenyl group, 2-propynyl, methoxy, decyloxymethyl or decylthiomethyl. 3. A pest control composition comprising as an active ingredient a cyclopropanecarboxylate as claimed in claim 1 or 2 4. A pest control method comprising applying an effective amount of a cyclopropanecarboxylate as in claim 1 or 2 to a pest or the pest habitat. 5. - for use in manufacturing as claimed in claim 1 or A method of a two-part cyclopropanecarboxylate comprising the steps of: reacting a compound of formula (6) in the presence of an oxide of manganese or cerium: (6) 與過碘酸鹽反應而獲得式（3)之羧酸：(6) reacting with periodate to obtain the carboxylic acid of formula (3): (3) 以及使式（3)之羧酸與式（2)之醇反應而獲得該環丙烷 42 320738 200932723 羧酸酯：(3) and reacting a carboxylic acid of the formula (3) with an alcohol of the formula (2) to obtain the cyclopropane 42 320738 200932723 Carboxylic acid ester: 式中，R1表示氳原子、氟原子、C卜C4烷基、C2-C4烯 基、C2-C4炔基、C1-C4烷氧基、（C1-C4烷基）氧基曱 基或（C1-C4烷基）硫曱基。 ❹ 43 320738 200932723 四、指定代表圖：本案無圖式。 (一) 本案指定代表圖為：第（ ）圖。 (二) 本代表圖之元件符藥簡單說明： ❹ 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式Wherein R1 represents a halogen atom, a fluorine atom, a C-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, a (C1-C4 alkyl)oxydecyl group or (C1) -C4 alkyl)thiol group. ❹ 43 320738 200932723 IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: ( ). (2) A brief description of the components of this representative figure: ❹ 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. (1) ❹ 2 320738(1) ❹ 2 320738
TW097143796A 2007-11-15 2008-11-13 Cyclopropanecarboxylate and use thereof TW200932723A (en)

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