US005872137A United States Patent [19] [11] Patent Number: 5,872,137 Sakamoto et al. [45] Date of Patent: Feb. 16, 1999

[54] DIHALOPROPENE COMPOUNDS, 4,061,683 12/1977 Karrer . INSECTICIDAL/ACARICIDAL AGENTS 4,496,440 1/1985 Campbell et al. . CONTAINING SAME, AND INTERMEDIATES 4,772,633 9/1988 Matsuo et al. . FOR THEIR PRODUCTION 5,302,619 4/1994 Shuto et al. . 5,530,015 6/1996 Sakamoto et al. . [75] Inventors: Noriyasu Sakamoto, Osaka; Masaya FOREIGN PATENT DOCUMENTS Suzuki, TakaraZuka; Kazunori Tsushima, Sanda; Kimitoshi Umeda, 0203798 12/ 1986 European Pat. Off. . TakaraZuka, all of Japan 0218543 4/1987 European Pat. Off. . 0227369 7/1987 European Pat. Off. . [73] Assignee: Sumitomo Chemical Company, 55—120565 9/1980 Japan . 56—029504 3/1981 Japan . Limited, Osaka, Japan 1420171 1/1976 United Kingdom . 1424211 2/1976 United Kingdom . [21] Appl. No.: 917,372 1578412 11/1980 United Kingdom . [22] Filed: Aug. 26, 1997 OTHER PUBLICATIONS Related US. Application Data Head et al., J. Chem. Soc. (C), pp. 871—874 (1971). Dorman, J. Org. Chem., vol. 31, pp.3666—3671 (1966). [63] Continuation of Ser. No. 624,488, ?led as PCT/JP95/01439 English language abstract of Japanese Patent No. Jul. 20, 1995, abandoned. 55—120565 Aug. 3, 1979. [30] Foreign Application Priority Data English language abstract of Japanese Patent No. 56—029504 Aug. 16, 1979. Aug. 4, 1994 [JP] Japan ...... 6-183461 Oct. 7, 1994 [JP] Japan .. 6-243931 Primary Examiner—Gary Geist Apr. 14, 1995 [JP] Japan ...... 7-089737 Assistant Examiner—Sreeni Padmanabhan [51] Int. Cl.6 ...... A01N 43/40 Attorney, Agent, or Firm—Birch, SteWart, Kolasch & Birch, LLP [52] US. Cl...... 514/345; 568/649; 568/674; 424/406 [57] ABSTRACT [58] Field of Search ...... 568/649, 674; 424/406; 514/345 The dihalopropene compounds of the general formula [I] have excellent insecticidal/acaricidal activity, so that they [56] References Cited are satisfactorily effective for the control of noxious insects, mites and ticks. U.S. PATENT DOCUMENTS 4,048,235 9/1977 Karrer. 92 Claims, No Drawings 5,872,137 1 2 DIHALOPROPENE COMPOUNDS, -continued INSECTICIDAL/ACARICIDAL AGENTS R10 IIU Q3 CONTAINING SAME, AND INTERMEDIATES CH, FOR THEIR PRODUCTION (R9)l R11 P This application is a continuation of application Ser. No. Q4 08/624,488 ?led on Apr. 4, 1996, noW abandoned. This is the US. National stage Application of PCT/JP95/ 01439 ?led Jul. 20, 1995 noW WO96/04228 published Feb. (R4)m 10 15, 1996. 1. Technical Field The present invention relates to dihalopropene compounds, insecticidal/acaricidal agents containing these Q5 compounds as active ingredients, for their production. 15 2. Background Art As disclosed in JP-A 48-86835/1973 and JP-A 49-1526/ (R9) 0 1974, for example, it is Well knoWn that some kinds of propene compounds can be used as an active ingredient of R15 R10 IIU Q6 insecticides. A CH In vieW of their insecticidal/acaricidal activity, it cannot (R9)! R16 S Rn p alWays be said that these compounds are satisfactorily active for the control of noXious insects, mites and ticks. R15 R F R10 IIU Q7 Disclosure of Invention 25 0 Z1 c—o — CH, (R9)l R16 S h R11 P The present inventors have intensively studied to ?nd a compound having excellent insecticidal/acaricidal activity. R5 0 R10 R7 Q8 As a result, they have found that particular dihalopropene compounds have satisfactory insecticidal/acaricidal activity (R4)l ®i3=c(rr6)—d:—o {11 P (IIH for the control of noXious insects, mites and ticks, thereby completing the present invention. R15 IFS R10 IIU Q9 That is, the present invention provides a dihalopropene 0 A c =C(R6) CH, compound (hereinafter referred to as the present compound) (R9)! R16 S Rn p of the general formula: 35 QlU R2 [1] (R14)r

Wherein R4 and R12 are independently halogen, C1—C4 alkyl, Wherein R1 is C1—C1O alkyl, C1—C5 haloalkyl, C2—C1O C1—C3 haloalkyl, C1—C3 alkoXy or C1—C3 haloalkoXy, alkenyl, C2—C6 haloalkenyl, C3—C9 alkynyl, C3—C5 45 R5 and R6 are independently hydrogen, C1—C3 alkyl, haloalkynyl, C2—C7 alkoXyalkyl, (C1—C3) alkoXy (C1—C7) tri?uoromethyl or halogen, carbonylalkyl, C2—C7 alkylthioalkyl; C3—C6 cycloalkyl R7 is hydrogen or C1—C3 alkyl, Which may be substituted With C1—C4 alkyl, C1—C3 alkoXy or C1—C3 haloalkoXy; C4—C9 cycloalkylalkyl Which may be R8 is hydrogen, halogen or methyl, substituted With C1—C4 alkyl; C5—C6 cycloalkenyl Which R9 is halogen, cyano, nitro, hydroXy, penta?uorosulfanyl may be substituted With C1—C4 alkyl; C6—C8 cycloalkeny (FSS), C1—C8 alkyl, C1—C3 haloalkyl, C1—C8 alkoXy, lalkyl Which may be substituted With C1—C4 alkyl; or Q1, Q2, haloalkoXy, C1—C3 alkylthio, C1—C3 haloalkylthio, Q3, Q4, Q5, Q6, Q7, Q8, Q9 or Q1O of the general formula: C3—C6 alkenyloXy, C3—C6 haloalkenyloXy, C1—C3 hydroXyalkyl, C2—C4 alkenyl, C2—C4 haloalkenyl, 55 C2—C4 alkynyl, C2—C4 alkynyloXy, C2—C4 haloalkynyl, IFS R10 IIU Q1 C2—C4 haloalkynyloXy, C2—C4 alkoXyalkyl, C2—C4 c =C(R6) CH, alkylthioalkyl, C3—C6 cycloalkyl, C5—C6 cycloalkenyl, 11 (R4)! R P C2—C5 alkoXycarbonyl, C3—C6 cycloalkyloXy, C5—C6 cycloalkenyloXy; phenyl Which may be substituted R10 IIU Q2 With halogen, C1—C4 alkyl, C1—C3 haloalkyl, C1—C3 CH alkoXy, C1—C3 haloalkoXy, C3—C6 alkenyloXy or C3—C6 haloalkenyloXy; phenoXy Which may be substituted (Rom R11 With halogen, C1—C4 alkyl, C1—C3 haloalkyl, C1—C3 alkoXy, C1—C3 haloalkoXy, C3—C6 alkenyloXy or C3—C6 R8 65 haloalkenyloXy; benZyl Which may be substituted With halogen, C1—C4 alkyl, C1—C3 haloalkyl, C1—C3 alkoXy, C1—C3 haloalkoXy, C3—C6 alkenyloXy or C3—C6 5,872,137 3 haloalkenyloxy; benZyloxy Which may be substituted a compound of the general formula: With halogen, C1—C4 alkyl, C1—C3 haloalkyl, C1—C3 alkoxy, C1—C3 haloalkoxy, C3—C6 alkenyloxy or C3—C6 R2 [III] haloalkenyloxy; or pyridyloxy Which may be substi tuted With halogen, C1—C4 alkyl, C1—C3 haloalkyl, HO OCH2CH=CX2 C1—C3 alkoxy, C1—C3 haloalkoxy, C3—C6 alkenyloxy or C3—C6 haloalkenyloxy; or R3 When 1 is an integer of 2 to 5, tWo adjacent Rg’s are taken together to form trimethylene, tetramethylene, methyl Wherein R2 and R3 are independently halogen, C1—C3 alkyl enedioxy Which may be substituted With halogen or or C1—C3 haloalkyl, and X’s are independently chlorine or C1—C3 alkyl; or ethylenedioxy Which may be substi bromine; tuted With halogen or C1—C3 alkyl, a compound of the general formula: R10, R11, R15 and R16 are independently hydrogen, C1—C3 15 R21 [IV] alkyl or tri?uoromethyl,

A is oxygen, 5(0),, NR13, C(=G1)G2 or G1C(=G2) (CH2), —c—o OH Wherein G1 and G2 are independently oxygen or sulfur, H R13 is hydrogen, acetyl or C1—C3 alkyl, and t is an (R19)l 2 integer of 0 to 2, R22 Z1 is oxygen, sulfur or NR17 Wherein R17 is hydrogen, Wherein R21 and R22 are independently halogen or C1—C3 acetyl or C1—C3 alkyl, alkyl, R19 is halogen, C1—C3 haloalkoxy or tri?uoromethyl, u is 1 to 4, and l is an integer of 0 to 5; 1 is an integer of 0 to 5, a compound of the general formula: m is an integer of 0 to 4, R2 [V] n is an integer of 1 or 2, p is an integer of 0 to 6, R10 IIU q is an integer of 0 to 3, and Q B CH—O OH (R20)l R11 6 s is an integer of 1 to 6, R3 R2, R3 and R14 are independently halogen, C1—C3 haloalkyl or C1—C3 alkyl, Wherein R2 and R3 are independently halogen, C1—C3 alkyl or C1—C3 haloalkyl, R7 is hydrogen or C1—C3 alkyl, R10 and r is an integer of 0 to 2, R11 are independently hydrogen, C1—C3 alkyl or X’s are independently chlorine or bromine, tri?uoromethyl, R20 is halogen, C1—C3 alkoxy, tri?uorom ethyl or C1—C3 haloalkoxy, l is an integer of 0 to 5, and e is Y is oxygen, NH or sulfur, and an integer of 1 to 4; and particularly, a compound Wherein Z is oxygen, sulfur or NR13 Wherein R13 is hydrogen, B is oxygen; a compound Wherein R2 and R3 are indepen acetyl or C1—C3 alkyl. dently halogen or C1—C3 alkyl, R7, R10 and R11 are all The present invention also provides an insecticidal/ hydrogen, e is 1 to 4, and B is oxygen, 5(0); or NR13 acaricidal agent containing the above dihalopropene com Wherein R13 is hydrogen, acetyl or C1—C3 alkyl, and t is an integer of 0 to 2. pound as an active ingredient. 45 The present invention further provides the folloWing DETAILED DESCRIPTION OF THE compounds Which are useful as intermediates for producing INVENTION some of the present compounds: The variables in the above formulae for the present a compound of the general formula: compounds and their intermediates can take the folloWing speci?c examples. R2 [II] Examples of the halogen atom represented by R2, R3, R4, R5, R6, R8, R9 or R12 or present in R9 are ?uorine, chlorine, bromine or iodine. Examples of the C1—C1O alkyl group represented by R1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert pentyl, n-hexyl, n-heptyl, isohexyl, n-octyl, n-nonyl, n-decyl, 3-n-pentyl, 2-ethylbutyl, 1-methylpentyl, Wherein R2 and R3 are independently halogen, C1—C3 alkyl a O 1-ethylbutyl, 3-methylpentyl, 1,3-dimethylbutyl, or C1—C3 haloalkyl, R7 is hydrogen or C1—C3 alkyl, R10 and 1-methylheptyl and 1-methyloctyl. R11 are independently hydrogen, C1—C3 alkyl or Examples of the C1—C4 alkyl group present in R1 or R9, tri?uoromethyl, X’s are independently chlorine or bromine, or represented by R4 or R12, are methyl, ethyl, n-propyl, L1 is hydroxy, halogen, methanesulfonyloxy or isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. p-toluenesulfonyloxy, and e is an integer of 2 to 4; and Examples of the C1—C3 alkyl group represented by R2, R3, particularly, a compound Wherein R7, R10 and R11 are all R5, R6, R7, R10, R11, R13, R14, R15 or R16 are methyl, ethyl, hydrogen, and e is 2 or 3; n-propyl and isopropyl.

5,872,137 7 8 butyloxycyclopentyl, 2-tert-butyloxycyclopentyl, bromodi?uoromethylthio, 2,2,2-tri?uoroethylthio, 2-chloro cyclopentyl, 3-methylcyclopentyl, 2-methylcyclopentyl, 1,1,2-tri?uoroethylthio, 2-bromo-1,1,2-tri?uoroethylthio, 3-methoxycyclohexyl, 3-ethoxycyclohexyl, 1,1,2,Z-tetra?uoroethylthio, 2-chloroethylthio, 3-propoxycyclohexyl, 3-isopropoxycyclohexyl, 2-?uoroethylthio, 2-bromoethylthio, 3-?uoropropylthio, 3-butoxycyclohexyl, 3-isobutyloxycyclohexyl, 3-sec 3-chloropropylthio, (3-bromopropyl)thio, 2,2,3,3,3 butyloxycyclohexyl, 3-tert-butyloxycyclohexyl, penta?uoropropylthio and 3,3,3-tri?uoropropylthio. 4-methoxycyclohexyl, 4-ethoxycyclohexyl, Examples of the C3—C6 alkenyloxy group represented by 4-propoxycyclohexyl, 4-isopropoxycyclohexyl, R9 are allyloxy, 2-methylallyloxy, 2-butenyloxy, 3-methyl 4-butoxycyclohexyl, 4-isobutyloxycyclohexyl, 4-sec 2-butenyloxy, 2-methyl-2-butenyloxy, 2-pentenyloxy and butyloxycyclohexyl and 4-tert-butyloxycyclohexyl. 2-hexenyloxy. Examples of the C4—C9 cycloalkylalkyl group represented by R1, Which may be substituted With C1—C4 alkyl, are Examples of the C3—C6 haloalkenyloxy group represented cyclopropylmethyl, cyclobutylmethyl, l-cyclopropylethyl, by R9 are 3,3-dichloroallyloxy, 3,3-dibromoallyloxy, 2,3 2-methylcyclopropylmethyl, 2-(2-methylcyclopropyl)ethyl, dichloroallyloxy, 2,3-dibromoallyloxy, 2-chloro-2 propenyloxy, 3-chloro-2-propenyloxy, 2-bromo-2 cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl, 15 3-cyclopentylpropyl and 3-cyclohexylpropyl. propenyloxy and 3-chloro-2-butenyloxy. Examples of the C5—C6 cycloalkenyl group represented Examples of the C1—C3 hydroxyalkyl group represented by R1, Which may be substituted With C1—C4 alkyl, are by R9 are hydroxymethyl, 2-hydroxyethyl, l-hydroxyethyl, 2-cyclohexenyl, 3,5,5-trimethyl-2-cyclohexenyl, 3-methyl 3-hydroxypropyl, 2-hydropropyl and l-hydroxypropyl. 2-cyclohexenyl, 3-cyclohexenyl, 2-cyclopentenyl and Examples of the C2—C5 alkoxycarbonyl group represented 3-cyclopentenyl. by R9 are methoxycarbonyl, ethoxycarbonyl, Examples of the C6—C8 cycloalkenylalkyl group repre n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sented by R1, Which may be substituted With C1—C4 alkyl, isobutoxycarbonyl, sec-butoxycarbonyl and tert are (1-cyclopentenyl)methyl, (3-cyclohexenyl)methyl and butoxycarbonyl. 2-(3-cyclohexenyl)ethyl. 25 The folloWing are preferred examples of the present Examples of the C3—C6 cycloalkyl group represented by compound: R9 are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. dihalopropene compounds Wherein R2 and R3 are inde Examples of the C5—C6 cycloalkenyl group represented pendently halogen or C1—C3 alkyl, and r is 0; by R9 are l-cyclopentenyl, 2-cyclopentenyl, dihalopropene compounds Wherein R2 and R3 are inde 3-cyclopentenyl, l-cyclohexenyl, 2-cyclohexenyl and pendently chlorine, bromine, methyl, ethyl or 3-cyclohexenyl. isopropyl, and r is 0; Examples of the C3—C6 cycloalkyloxy group represented dihalopropene compounds Wherein R2 and R3 are both by R9 are cyclopropyloxy, cyclobutyloxy, cyclopentyloxy chlorine, and r is 0; and cyclohexyloxy. dihalopropene compounds Wherein R2 is chlorine, R3 is Examples of the C5—C6 cycloalkenyloxy group repre 35 methyl, and r is 0; sented by R9 are l-cyclopentenyloxy, 2-cyclopentenyloxy, dihalopropene compounds Wherein R2 is ethyl, R3 is 3-cyclopentenyloxy, l-cyclohexenyloxy, methyl, and r is 0; 2-cyclohexenyloxy and 3-cyclohexenyloxy. dihalopropene compounds Wherein R2 is ethyl, R3 is Examples of the C1—C3 alkoxy group present in R1 or R9, methyl, and r is 0; or represented by R4 or R12 are methoxy, ethoxy, n-propoxy dihalopropene compounds Wherein R2 and R3 are both and isopropoxy. bromine, and r is 0; Examples of the (C1—C3)alkoxy(C1—C7)carbonylalkyl group represented by R1 are 1-(ethoxycarbonyl)methyl, dihalopropene compounds Wherein R2 and R3 are both 1-(methoxycarbonyl)methyl, 1-(n-propoxycarbonyl)methyl, ethyl, and r is 0; 2-(methoxycarbonyl)ethyl, 1-(isopropoxycarbonyl)methyl, 45 dihalopropene compounds Wherein R2 and R3 are inde 3-(methoxycarbonyl)propyl, 4-(methoxycarbonyl)butyl, pendently halogen or C1—C3 alkyl, r is 1 or 2, and R14 5-(methoxycarbonyl)pentyl, 6-(methoxycarbonyl)hexyl and is halogen or C1—C3 alkyl; 7-(methoxycarbonyl)heptyl. dihalopropene compounds Wherein R2 and R3 are inde Examples of the C1—C8 alkoxy group represented by R9 pendently halogen or C1—C3 alkyl, r is 1 or 2, and R14 are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec is halogen; butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isopentyloxy, dihalopropene compounds Wherein Y and Z are both neopentyloxy, tert-pentyloxy, (1-ethylpropyl)oxy, oxygen; n-hexyloxy, octyloxy and n-heptyloxy. dihalopropene compounds Wherein R1 is Q3; Examples of the C1—C3 haloalkoxy group present in R1 or 55 dihalopropene compounds Wherein R1 is Q3, p is 0, and represented by R4 or R9 are tri?uoromethoxy, R9 is halogen, C1—C4 alkyl, C1—C3 haloalkyl, C1—C4 di?uoromethoxy, bromodi?uoromethoxy, 2-?uoroethoxy, alkoxy, C1—C3 haloalkoxy, C1—C3 alkylthio, C1—C3 2,2,2-tri?uoroethoxy, 2-chloroethoxy, 2-bromoethoxy, haloalkylthio, cyano, nitro or 3,4-methylenedioxy; 2-chloro-1,1,2-tri?uoroethoxy, 2-bromo-1,1,2 dihalopropene compounds Wherein R1 is Q3, p is, 0, R9 is tri?uoroethoxy, 1,1,2,2-tetra?uoroethoxy, 1,2,2,3,3,3 phenyl Which may be substituted With halogen, hexa?uoropropoxy, 3-?uoropropoxy, 3-chloropropoxy, penta?uorosulfanyl, C1—C4 alkyl, C1—C3 haloalkyl, 3-bromopropoxy, 2,2,3,3,3-penta?uoropropoxy, 3,3,3 C1—C3 alkoxy or C1—C3 haloalkoxy; benZyl Which may tri?uoropropoxy and 1,1,2,2,2-penta?uoroethoxy. be substituted With halogen, penta?uorosulfanyl, Examples of the C1—C3 alkylthio group represented by R9 C1—C4 alkyl, C1—C3 haloalkyl, C1—C3 alkoxy or C1—C3 are methylthio, ethylthio, n-propylthio and isopropylthio. 65 haloalkoxy; phenoxy Which may be substituted With Examples of the C1—C3 haloalkylthio group represented halogen, penta?uorosulfanyl, C1—C4 alkyl, C1—C3 by R9 are tri?uoromethylthio, di?uoromethylthio, haloalkyl, C1—C3 alkoxy or C1—C3 haloalkoxy; or ben 5,872,137 9 10 Zyloxy Which may be substituted With halogen, Examples of the solvent that can be used are ketones such penta?uorosulfanyl, C1—C4 alkyl, C1—C3 haloalkyl, as acetone, methyl ethyl ketone and cyclohexanone; ethers C1—C3 alkoxy or C1—C3 haloalkoxy; such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane and dihalopropene compounds wherein R1 is Q3, p is 1 to 3, dialkyl (e.g., C1—C4) ether (e.g., diethyl ether, diisopropyl R10 and R11 are both hydrogen, and R9 is halogen, ether); N,N-dimethylformamide, dimethylsulfoxide, hexam tri?uoromethyl, penta?uorosulfanyl or C1—C3 ethylphophoric triamide, sulforane, acetonitrile, haloalkoxy; nitromethane; halogenated hydrocarbons such as dihalopropene compounds Wherein R1 is Q5; dichloromethane, chloroform, 1,2-dichloroethane and chlo dihalopropene compounds Wherein R1 is Q5, p is 1 to 4, robenZene; hydrocarbons such as toluene, benZene and R10 and R11 are both hydrogen, and R9 is halogen, 10 xylene; and Water. If necessary, a mixture of these solvents tri?uoromethyl, C1—C3 alkoxy, C1—C3 haloalkoxy, pen can be used. ta?uorosulfanyl or penta?uorosulfanyl; Examples of the base Which can be used are hydroxides of alkali metals or alkaline earth metals, such as lithium dihalopropene compounds Wherein R1 is Q5, p is 2 or 3, hydroxide, sodium hydroxide, potassium hydroxide and R10 and R11 are both hydrogen, R9 is halogen, 15 calcium hydroxide; carbonates of alkali metals or alkaline tri?uoromethyl, isopropyloxy, C1—C3 haloalkoxy, pen earth metals, such as lithium carbonate, potassium ta?uorosulfanyl or di?uoromethylenedioxy, and A is carbonate, sodium carbonate and calcium carbonate; oxygen; hydrides of alkali metals or alkaline earth metals, such as dihalopropene compounds Wherein R1 is Q5, p is 2 or 3, lithium hydride, sodium hydride, potassium hydride and R10 and R11 are both hydrogen, R9 is halogen, 20 calcium hydride; alkali metal alkoxides (e.g., C1—C4), such tri?uoromethyl, isopropyloxy or C1—C3 haloalkoxy, as sodium methoxide, sodium ethoxide and potassium tert and A is oxygen; and butoxide; and organic bases such as triethylamine and pyri dihalopropene compounds Wherein R1 is C1—C1O alkyl, dine. If necessary, catalysts such as ammonium salts (e.g., C1—C5 haloalkyl, C2—C1O alkenyl, C2—C6 haloalkenyl, triethylbenZylammonium chloride) may be added to the C3—C9 alkynyl, C3—C5 haloalkynyl, C2—C7 25 reaction system at a ratio of 0.01 to 1 mole per mole of the alkoxyalkyl, alkyl, (C1—C3)alkoxy(C1—C7) compound of the general formula [VI]. carbonylalkyl or C2—C7 alkylthioalkyl; C3—C6 The reaction temperature is usually set Within the range of cycloalkyl Which may be substituted With C1—C4 alkyl, —20° C. to 150° C. or the boiling point of a solvent used in C1—C3 alkoxy or C1—C3 haloalkoxy; C4—C9 cycloalky the reaction, preferably —5° C. to 100° C. or the boiling point lalkyl Which may be substituted With C1—C4 alkyl; 30 of a solvent used in the reaction. C5—C6 cycloalkenyl Which may be substituted With The molar ratio of the starting materials and bases to be C1—C4 alkyl; or C6—C8 cycloalkenylalkyl Which may be used in the reaction can be freely determined, but it is substituted With C1—C4 alkyl. favorable to effect the reaction at an equimolar ratio or a The folloWing are particularly preferred examples of the ratio closer thereto. present compound Wherein numbers in parentheses are the 35 After completion of the reaction, the reaction mixture is corresponding compound numbers used beloW: subjected to ordinary post-treatments such as organic sol (100) 3,5—Dichloro—4-(3-(4-tri?uoromethoxyphenoxy) vent extraction and concentration, and the desired com propyloxy)-1-(3,3-dichloro-2-propenyloxy)benZene; pound of the present invention can be isolated. Further, (166) 3,5—Dichloro—4-(3-(4-tri?uoromethylphenoxy) propyl puri?cation can be carried out, if necessary, by an ordinary oxy)-1-(3,3-dichloro-2-propenyloxy)benZene; 40 technique such as chromatography, distillation or recrystal (203) 3,5—Dichloro—4-(4-(4-isopropyloxyphenoxy)butyloxy) liZation. -1-(3,3-dichloro-2-propenyloxy)benZene; (Production Process B for the present compounds Wherein (222) 3,5—Dichloro—4-(4-(4-chlorophenoxy)butyloxy)-1-(3, Y is oxygen) 3-dichloro-2-propenyloxy)benZene; and In this process, a compound of the general formula [VI] (284) 3-Ethyl-5-methyl-4-(3-(4-tri?uoromethylphenoxy) 45 is reacted With an alcohol compound of the general formula: propyloxy)-1-(3,3-dichloro-2-propenyloxy)benZene. The present compounds can be produced, for example, by the folloWing production processes A-G. Wherein X is as de?ned above. (Production Process A) The reaction is preferably effected in an inert solvent, if In this process, a compound of the general formula: 50 necessary, in the presence of a suitable dehydrating agent. Examples of the dehydrating agent Which can be used are R2 [VI] dicyclohexylcarbodiimide, and dialkyl (e.g., C1—C4) aZodi (R14)r carboxylates (e.g. diethylaZodicarboxylate, diisopropylaZodicarboxylate)-trialkyl (e.g., C1—C2O) phos R1—Z YH 55 phine or triarylphosphine (e.g., triphenylphosphine, trioctylphosphine, tributylphosphine). R3 Examples of the solvent Which can be used are hydrocar bons such as benZene, xylene and toluene; ethers such as Wherein R1, R2, R3, R 14, r, Y and Z are each as de?ned diethyl ether, diisopropyl ether, tetrahydrofuran and diox above, is reacted With a halide compound of the general 60 ane; and halogenated hydrocarbons such as carbon formula: tetrachloride, dichloromethane, chlorobenZene and dichlo robenZene. The reaction temperature is usually set Within the range of Wherein X is as de?ned above and L is halogen (e.g., —20° C. to 200° C. or the boiling point of a solvent used in chlorine, bromine, iodine), mesyloxy or tosyloxy. 65 the reaction. The reaction is preferably effected in an inert solvent in The molar ratio of the starting materials and dehydrating the presence of a suitable base. agents to be used in the reaction can be freely determined, 5,872,137 11 12 but it is favorable to effect the reaction at an equimolar ratio Wherein R1 and L are each as de?ned above. or a ratio closer thereto. The reaction is preferably effected in an inert solvent in After completion of the reaction, the reaction mixture is the presence of a suitable base. subjected to ordinary post-treatments such as organic sol Examples of the solvent Which can be used are ketones vent extraction and concentration, and the desired com such as acetone, methyl ethyl ketone and cyclohexanone; pound of the present invention can be isolated. Further, ethers such as 1,2-dimethoxyethane, tetrahydrofuran, diox puri?cation can be carried out by an ordinary technique such ane and dialkyl (e.g., C1—C4) ethers (e.g., diethyl ether, as chromatography, distillation or recrystalliZation. diisopropyl ether); N,N-dimethylformamide, (Production Process C for the present compounds Wherein dimethylsulfoxide, hexamethylphosphoric triamide, Y is oxygen) 10 sulforane, acetonitrile, nitromethane; halogenated hydrocar In this process, an aldehyde compound of the general bons such as dichloromethane, chloroform, 1,2 formula: dichloroethane and chlorobenZene; hydrocarbons such as toluene, benZene and xylene; and Water. If necessary, a mixture of these solvents can be used. 15 Examples of the base Which can be used are hydroxides of alkali metals or alkaline earth metals, such as lithium R1 —Z OCHZCHO hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals, such as lithium carbonate, potassium 20 carbonate, sodium carbonate and calcium carbonate; Wherein R1, R2, R3, R14, r and Z are each as de?ned above, hydrides of alkali metals or alkaline earth metals, such as is reacted With carbon tetrachloride or carbon tetrabromide. lithium hydride, sodium hydride, potassium hydride and The reaction is preferably effected in an inert solvent in calcium hydride; alkali metal alkoxides (e.g., C1—C4) such the presence of a suitable trialkylphosphine or as sodium methoxide, sodium ethoxide and potassium tert triarylphosphine, and if necessary, in the presence of metal 25 butoxide; organic bases such as triethylamine and pyridine. Zinc. If necessary, catalysts such as ammonium salts (e.g., trieth Examples of the solvent Which can be used are hydrocar ylbenZylammonium chloride) may be added to the reaction bons such as benZene, xylene and toluene; ethers such as system at a ratio of 0.01 to 1 mole per mole of the compound diethyl ether, diisopropyl ether, tetrahydrofuran and diox of the general formula ane; and halogenated hydrocarbons (exclusive of carbon 30 The reaction temperature is usually set Within the range of tetrabromide and carbon tetrachloride) such as —20° C. to 150° C. or the boiling point of a solvent used in dichloromethane, 1,2-dichloroethane and chlorobenZene. the reaction, preferably —5° C. to 100° C. or the boiling point The reaction temperature is usually set Within the range of of a solvent used in the reaction. —30° C. to 150° C. or the boiling point of a solvent used in The molar ratio of the starting materials and dehydrating the reaction. 35 agents to be used in the reaction can be freely determined, Examples of the trialkyl (e.g., C1—C2O) phosphine or but it is favorable to effect the reaction at an equimolar ratio triarylphosphine are triphenylphosphine and trioctylphos or a ratio closer thereto. phine. The metal Zinc Which is used, if necessary, is pref After completion of the reaction, the reaction mixture is erably in dust form. subjected to ordinary post-treatments such as organic sol The molar ratio of the starting materials and reagents to be 40 vent extraction and concentration, and the desired com used in the reaction can be freely determined, but the ratio pound of the present invention can be isolated. Further, is preferably such that carbon tetrabromide or tetrachloride, puri?cation can be carried out by an ordinary technique such trialkylphosphine or triarylphosphine, and Zinc are 2 moles, as chromatography, distillation or recrystalliZation. 2 or 4 moles (2 moles When Zinc is used), and 2 moles per (Production Process E for the present compounds Wherein mole of the aldehyde compound of the general formula [IX], 45 Y and Z are both oxygen) or it is favorable to effect the reaction at a ratio closer In this process, a compound of the general formula is thereto. reacted With an alcohol compound of the general formula: After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic sol vent extraction and concentration, and the desired com 50 Wherein R1 is as de?ned above. pound of the present invention can be isolated. Further, The reaction is preferably effected in an inert solvent, if puri?cation can be carried out by an ordinary technique such necessary, in the presence of a suitable dehydrating agent. as chromatography, distillation or recrystalliZation. Examples of the dehydrating agent Which can be used are (Production Process D for the present compounds Wherein dicyclohexylcarbodiimide, and dialkyl (e.g., C1—C4) aZodi Y and Z are both oxygen) 55 carboxylates (e.g., diethylaZodicarboxylate, In this process, a compound of the general formula: diisopropylaZodicarboxylate)-trialkyl (e.g., C1—C2O) phos phine or triarylphosphine (e.g., triphenylphosphine, R2 [X] trioctylphosphine, tributylphosphine). (R14) Examples of the solvent Which can be used are hydrocar 60 bons such as benZene, xylene and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and diox ane; and halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chlorobenZene and dichlo robenZene. Wherein R2, R3, R14, r, Y and Z are each as de?ned above, 65 The reaction temperature is usually set Within the range of is reacted With a compound of the general formula: —20° C. to 200° C. or the boiling point of a solvent used in the reaction. 5,872,137 13 14 The molar ratio of the materials and dehydrating agents to Examples of the base Which can be used are hydroxides be used in the reaction can be freely determined, but it is of alkali metals or alkaline earth metals, such as lithium favorable to effect the reaction at an equimolar ratio or a hydroxide, sodium hydroxide, potassium hydroxide and ratio closer thereto. calcium hydroxide; carbonates of alkali metals or alkaline After completion of the reaction, the reaction mixture is 5 earth metals, such as lithium carbonate, potassium subjected to ordinary post-treatments such as organic sol carbonate, sodium carbonate and calcium carbonate; vent extraction and concentration, and the desired com hydrides of alkali metals or alkaline earth metals, such as pound of the present invention can be isolated. Further, lithium hydride, sodium hydride, potassium hydride and puri?cation can be carried out by an ordinary technique such as chromatography, distillation or recrystalliZation. calcium hydride; alkali metal alkoxides (e.g., C1—C4) such (Production Process F for the present compounds Wherein as sodium methoxide, sodium ethoxide and potassium tert Y and Z are both oxygen and R1 is Q5 (With the proviso that butoxide; organic bases such as triethylamine and pyridine. A is A2), Q6 (With the proviso that A is A2), Q7, Q8 or Q1O If necessary, catalysts such as ammonium salts (e.g., trieth (With the proviso that A is A2) [Wherein A2 is oxygen, sulfur ylbenZylammonium chloride) may be added to the reaction or NR13 and R13 is as de?ned above]) system at a ratio of 0.01 to 1 mole per mole of the compound In this process, a compound of the general formula: of the general formula [XIII]. The reaction temperature is usually set Within the range of —20° C. to 150° C. or the boiling point of a solvent used in R10 R7 the reaction, preferably —5° C. to 100° C. or the boiling point 20 of a solvent used in the reaction. OCH2CH=CX2 R11 The molar ratio of the starting materials and dehydrating agents to be used in the reaction can be freely determined, R3 but it is favorable to effect the reaction at an equimolar ratio [XIII] or a ratio closer thereto. Wherein R2, R3, R7, R10, R11, R14, X, L, p and r are each as After completion of the reaction, the reaction mixture is de?ned above, is reacted With compound Q51, Q61, Q71, Q81 subjected to ordinary post-treatments such as organic sol or Q101 of the general formula: vent extraction and concentration, and the desired com pound of the present invention can be isolated. Further, Q51 puri?cation can be carried out by an ordinary technique such as chromatography, distillation or recrystalliZation. (Production Process G for the present compounds Wherein (R9)0% Y and Z are both oxygen and R1 is Q5 (With the proviso that R15 Q61 Ais oxygen), Q6 (With the proviso thatAis oxygen), Q7, Q8 or Q1O (With the proviso that A is oxygen)) — AZH In this process, a compound of the general formula: (R9), R“ S R2 (R14), [XIV] R10 R7 40 | HO CH-O OCH2CH=CX2 R11 P R3 45 Wherein R2, R3, R7, R10, R11, R14, X, p and r are each as de?ned above, is reacted With compound Q52, Q62, Q71, Q81 or Q102 of the general formula:

Q52 50 OH (R9) Wherein R4, R5, R6, R12, R15, R16, Z1, A21 , m, q and s are R15 Q62 each as de?ned above. The reaction is preferably effected in an inert solvent in 55 — OH the presence of a suitable base. (R9), R“ S Examples of the solvent Which can be used are ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as 1,2-dimethoxyethane, tetrahydrofuran, diox ane and dialkyl (e.g., C1—C4 ethers (e.g., diethyl ether, diisopropyl ether); N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulforane, acetonitrile, nitromethane; halogenated hydrocar bons such as dichloromethane, chloroform, 1,2 dichloroethane and chlorobenZene; hydrocarbons such as toluene, benZene and xylene; and Water. If necessary, a mixture of these solvents can be used. 5,872,137 15 -continued Q1U2

wherein R4, R5, R6, R12 R15, R16, Z11, m, q and s are each as de?ned above. The reaction is preferably effected in an inert solvent, if 10 necessary, in the presence of a suitable dehydrating agent. 021 H Examples of the dehydrating agent Which can be used are dicyclohexylcarbodiimide, and dialkyl (e.g., C1—C4) aZodi m carboxylates (e.g. , diethylaZodicarboxylate, diisopropylaZodicarboxylate)-trialkyl (e.g., C1—C2O) phos 15 PE | o phine or triarylphosphine (e.g., triphenylphosphine, trioctylphosphine, tributylphosphine). Examples of the solvent Which can be used are hydrocar bons such as benZene, xylene and toluene; ethers such as 7E | diethyl ether, diisopropyl ether, tetrahydrofuran and diox 5'11 ane; and halogenated hydrocarbons such as carbon OO tetrachloride, dichloromethane, chlorobenZene and dichlo robenZene.

The reaction temperature is usually set Within the range of 25 —20° C. to 200° C. or the boiling point of a solvent used in 7E | E0:: the reaction. OO The molar ratio of the materials and dehydrating agents to be used in the reaction can be freely determined, but it is favorable to effect the reaction at an equimolar ratio or a ratio closer thereto. 7E | E0:: After completion of the reaction, the reaction mixture is OO subjected to ordinary post-treatments such as organic sol vent extraction and concentration, and the desired com pound of the present invention can be isolated. Further, 35 puri?cation can be carried out by an ordinary technique such as chromatography, distillation or recrystalliZation. When the present compound has an asymmetry carbon atom, it is to be construed to include its optically active isomers ((+)-form and (—)-form) having biological activity and their mixtures at any ratio. When the present compound exhibits geometrical isomerism, it is to be construed to include its geometrical isomers (cis-form and transform) and their mixtures at any ratio. The folloWing are typical examples of the present com 45 pound (Wherein R1 is as shoWn in Tables 1 to 17), Which are not to be construed to limit the scope of the present inven PE | o tion. 021 H

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55

65 5,872,137 17 18 -continued -continued C1 PE | o WY

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5,872,137 21 22 -continued -continued C2H5

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