USOO5698702A United States Patent 19 11 Patent Number: 5,698,702 Sakamoto et al. 45 Date of Patent: Dec. 16, 1997

54) ENTERMEDIATE COMPOUND FOR USE IN 227369 7/1987 European Pat. Off.. PRODUCTION OFDHALOPROPENE 55-120565 9/1980 Japan. COMPOUND 56-0295.04 3/1981 Japan. 42011 1/1976 United Kingdom. 75 Inventors: Noriyasu Sakamoto, Nishinomiya; 1424211 2/1976 United Kingdom. Masaya Suzuki; Toshio Nagatomi, 1578412 11/1980 United Kingdom. both of Takarazuka; Kazunori OTHER PUBLICATIONS Tsushima, Sanda; Kimitoshi Umeda, Takarazuka, all of Japan Sagi K, Kagechika H, Fukasawa H, Hashimoto Y. Shudo K. Chem. Pharm. Bull. 44(6), 1273-1275, 1996. 73 Assignee: Sumitomo Chemical Company, Primary Examiner C. Warren Ivy Limited, Osaka-fu, Japan Assistant Examiner-Evelyn Huang Attorney, Agent, or Firm-Birch, Stewart, Kolasch & Birch, 21 Appl. No.: 600,179 LLP 22 Fied: Feb. 12, 1996 57 ABSTRACT Related U.S. Application Data There is disclosed a dihalopropene compound of the formula I: 62 Division of Ser. No. 325,597, Oct. 19, 1994, Pat. No. 5,530,015. (R), (R) 30 Foreign Application Priority Data Oct 19, 1993 JP Japan ...... 5-261380 Cy- Y (ty D-CHCH-CX (51) Int. Cl...... C07D 213/64; CO7D 213/643; N P = Q CO7D 43/23; CO7D 43/225 52 U.S. Cl...... 546/302; 546/304:568/639 wherein l is an integer of 1 to 5; m is an integer of 1 to 4; 58 Field of Search ...... 546/297,302, R's and R's are the same or different and are indepen 546/304:568/639 dently halogen or various other groups; D is oxygen; X's are the same or different and are independently chlorine or 56) References Cited bromine;Y is oxygen; Z, P and Q are the same or different and are independently nitrogen or CH, provided that P and U.S. PATENT DOCUMENTS Q are not simultaneously nitrogen, and when Y is sulfur, Z. 4.048235 9/1977 Karrer ...... 260/63 R is CH. Also disclosed is an insecticide?acaricide comprising 4,061683 12/1977 Karrer ...... 260/612 R the dihalopropene compound as an active ingredient. The 4,496,440 1/1985 Campbell et al...... 2O4f78 dihalopropene compound exhibits excellent insecticidal/ 4,772,633 9/1988 Matsuo ...... 514/717 acaricidal action. Further disclosed is an intermediate com pound for use in the production of the dihalopropene com FOREIGN PATENT DOCUMENTS pound. 0203798 12/1986 European Pat. Off.. 0218543 4/1987 European Pat. Off.. 8 Claims, No Drawings 5,698,702 1. 2 INTERMEDIATE COMPOUND FOR USE IN ene or tetramethylene; D is oxygen, NH or sulfur; X's are the PRODUCTION OF DHALOPROPENE same or different and are independently chlorine or bromine; COMPOUND Y is oxygen, NR, S(O)q, C(R), C=C(R) or CCCF), wherein R is hydrogen, C-C alkyl, trifluoroacetyl or This application is a divisional of application Ser. No. 5 acetyl, R's are the same or different and are independently 08/325,597, file on Oct. 19, 1994, U.S. Pat. No. 5,530,015 hydrogen or C-C alkyl, and q is an integer of 0 to 2; Z, P the entire contents of which are hereby incorporated by and Q are the same or different and are independently reference. nitrogen or CH, with the proviso that P and Q are not simultaneously nitrogen, and when Y is Sulfur, Zis CH, and FIELD OF THE INVENTION an insecticide?acaricide containing the dihalopropene com pound as an active ingredient. The present invention relates to a dihalopropene It is another object of the present invention to provide compound, and an insecticide?acaricide containing the diha intermediate compounds for use in the production of the lopropene compound as an active ingredient. It also relates above dihalopropene compound. to an intermediate compound for use in the production of the 15 dihalopropene compound. DESCRIPTION OF THE INVENTION DESCRIPTION OF THE RELATED ART For the substituents R and R, examples of the halogen are fluorine, chlorine, bromine and iodine. In the Japanese Patent Laid-open Publication Nos. For the substituent R', examples of the C-C alkyl are 48-86835/1973 and 49-1526/74, it is disclosed that certain methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, sec propene compounds can be used as an active ingredient of butyl, tert-butyl, n-penty, isopentyl, neopentyl, tert-penty, insecticides. n-hexyl, n-heptyl, tert-octyl, 3-n-penty and the like. However, these compounds are not necessarily sufficient For the substituents R' and R', examples of the C-C, as the active ingredient of insecticides/acaricides in view of haloalkyl are trifluoromethyl, difluoromethyl, insecticidal activity. 25 bromodifluoromethyl, 2,22-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 1-fluoroethyl, 1-chloroethyl, SUMMARY OF THE INVENTION 1-bromoethyl, 3,3,3,2,2-pentafluoro-n-propy, 3,3,3- Under these circumstances, the present inventors have trifluoro-n-propyl, 1-fluoro-n-propy, 2-chloro-n-propyl, studied intensively to find a compound having an excellent 3-bromo-n-propyl and the like. insecticidal/acaricidal activity. As a result, they have found 30 For the substituent R', examples of the C-C alkoxy are that particular dihalopropene compounds have an excellent methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec insecticidal/acaricidal activity, thereby completing the butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isopentyloxy, present invention. neopentyloxy, tert-pentyloxy, 3-n-pentyloxy, n-hexyloxy, That is, the present invention provides a dihalopropene n-heptyloxy and the like. compound of the formula I: 35 For the substituents R and R, examples of the C-C, haloalkoxy are trifluoromethoxy, difluoromethoxy, (R) (R) (T) bromodifluoromethoxy, 2-fluoroethoxy, 2,2,2- trifluoroethoxy, 2-chloroethoxy,2-bromoethoxy, 2-chloro-1, 1.2-trifluoroethoxy, 2-bromo-1,1,2-trifluoroethoxy, 1,122 tetrafluoroethoxy, 3,3,3,2,2,1-hexafluoro-n-propoxy, 3-fluoro-n-propoxy, 3-chloro-n-propoxy, 3-bromo-n- wherein. 1 is an integer of 1 to 5; m is an integer of 1 to 4; propoxy, 3,3,3,22-pentafluoro-n-propoxy, 3,3,3-n-propoxy, R" is halogen, cyano, acetamido, trifluoroacetamido, nitro, 2.2.2,1,1-pentafluoroethoxy and the like. C-Cs alkyl, C-C haloalkyl, C-C alkoxy, C-C- 45 For the substituent R', examples of the C-C alkylthio haloalkoxy, C-C alkylthio, C-C haloalkylthio, C-C are methylthio, ethylthio, n-propylthio, isopropylthio and alkenyloxy, C-C haloalkenyloxy, C-C hydroxyalkyl, the like. C-C alkenyl, C-C haloalkenyl, C-C alkynyl, C-C For the substituent R', examples of the C-C haloalky haloalkynyl, C-C alkynyloxy, C-C haloalkynyloxy, lthio are trifluoromethylthio, difluoromethylthio, C-C alkoxyalky1, C2-C alkylthioalkyl, Ca-C 50 bromodifluoromethylthio,2,2,2-trifluoroethylthio, 2-chloro cycloalkyl, C-C cycloalkenyl, C-C cycloalkyloxy, 1,1,2-trifluoroethylthio, 2-bromo-1,1,2-trifluoroethylthio, C-C cycloalkenyloxy, phenyl, pyridyloxy, phenoxy or 1,1,2,2-tetrafluoroethylthio, 2-chloroethylthio, benzyl, the last four of which may be optionally substituted 2-fluoroethylthio, 2-bromoethylthio, 3-fluoro-n-propylthio, with halogen, C-C alkyl, C-C alkoxy, C-C haloalkyl 3-chloro-n-propylthio, 3-bromo-n-propylthio, 3,3,3,2,2- or C-C haloalkoxy, with the proviso that when I is an 55 pentafluoro-n-propylthio, 3,3,3-trifluoro-n-propylthio and integer of 2 to 5, R's are the same or different, or two the like. adjacent R's may be combined together at their terminal For the Substituent R, examples of the C-C alkenyloxy ends to form trimethylene, tetramethylene, methylenedioxy, are allyloxy, 2-methylallyloxy, 2-butenyloxy, 3-methyl-2- ethylenedioxy or CH=CH-CH=CH; R is halogen, butenyloxy, 2-methyl-2-butenyloxy, 2-pentenyloxy, C-Cs alkyl, C-C haloalkyl, C-C alkoxy, C-C- 2-hexenyloxy and the like. haloalkoxy, C-C alkenyl, C-C haloalkenyl, C-C, For the substituent R', examples of the C-C haloalk alkynyl, C-C haloalkynyl, C-C alkoxyalkyl, C-C, enyloxy are 3,3-dichloroallyloxy, 3.3-dibromoallyloxy, 2,3- alkoxyimino, allyloxyimino, nitro or phenyl which may be dichloroallyloxy, 2,3-dibromoallyloxy, 2-chloro-2- optionally substituted with halogen, C-C alkyl or C-C, propenyloxy, 3-chloro-2-propenyloxy, 2-bromo-2- alkoxy, with the proviso that when m is an integer of 2 to 4, 65 propenyloxy, 3-chloro-2-butenyloxy and the like. R’s are the same or different, or two adjacent R's may be For the substituent R', examples of the C-C hydroxy combined together at their terminal ends to form trimethyl alkyl are hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 5,698,702 3 4 3-hydroxy-n-propyl, 2-hydroxy-n-propyl, 1-hydroxy-n- tuted with C-C alkoxy, examples of the C-C alkoxy are propyl and the like. methoxy, ethoxy, n-propoxy and i-propoxy. For the substituents R' and R, examples of the C-C, For the substituent R, examples of the C-C alkoxy alkenyl are vinyl, isopropenyl, n-1-propenyl, 2-methyl-1- imino are methoxyimino, ethoxyimino, n-propoxyimino, propenyl, 1-methyl-1-propenyl, ally, 2-methylpropenyl, isopropoxyimino and the like. 2-n-butenyl and the like. Examples of the C-C alkoxy which may be optionally For the substituents R' and R, examples of the C-C, present on the phenyl for the substituent R are methoxy, haloalkenyl are 2,2-dichloroethenyl, 2,2-dibromoethenyl, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, sec-butoxy, 3,3-dichloroally, 3,3-dibromoallyl, 2,3-dichloroallyl, 2,3- isobutoxy, tert-butoxy, n-pentyloxy, 3-n-pentyloxy, dibromoallyl, 2-chloro-2-propenyl, 3-chloro-2-propenyl, 10 isopentyloxy, neopentyloxy, tert-pentyloxy group and the 2-bromo-2-propenyl, 3-chloro-2-butenyl and the like. like. For the substituents R' and R, examples of the C-C, For the substituent R, examples of the C-C alkyl are alkynyl are ethynyl, 1-propynyl, 2-propenyl, 1-methyl-2- methyl, n-propyl, ethyl, isopropyl group and the like. propynyl and the like. For the substituents R' and R, examples of the C-C, For the substituents R and R', examples of the C-C, 15 alkyl are methyl or ethyl. haloalkynyl are chloroethynyl, bromoethynyl, iodoethynyl, Among the dihalopropene compounds of the present 3-chloro-2-propynyl, 3-bromo-2-propynyl, 3-iodo-2- invention, preferable compounds are those defined as foll propynyl, 1-methyl-3-chloro-2-propynyl, 1-methyl-3- lows: R' is halogen, C-C alkyl, C-C haloalkyl, C-C, bromo-2-propynyl, 1-methyl-3-iodo-2-propynyl and the alkoxy, C-C haloalkoxy, C-C alkenyloxy, Ca-C like. 20 haloalkenyloxy, C-C cycloalkyl, phenyl, pyridyloxy, phe For the substituent R', examples of the C-C alkynyloxy noxy or benzyl, the last four of which may be optionally are 2-propynyloxy, 1-methyl-2-propynyloxy, 3-butynyloxy, substituted with halogen C-C alkyl, C-C alkoxy, C-C, 2-hexynyloxy, 3-hexynyloxy, 2-methyl-3-bytynyloxy, haloalkyl or C-C haloalkoxy, with the proviso that when 1-methyl-3-bytynyloxy and 2-pentynyloxy. 25 lis an integer of 2 to 5, R's are the same or different, or two For the substituent R, examples of the C-C haloalky adjacent R's may be combined together at their terminal nyloxy are 3-chloro- 2-propynyloxy, 3-bromo-2- ends to form trimethylene, tetramethylene, methylenedioxy, propynyloxy, 1-methyl-3-chloro-2-propynyloxy, 1-methyl ethylenedioxy or CH=CH-CH=CH;R is halogen, nitro, 3-bromo-2-propynyloxy, 4-chloro-3-bytynyloxy, 4-bromo C1-C5 alkyl, C-C haloalkyl, C-C alkenyl, C-C, 3-bytynyloxy, 2-methyl-4-chloro-3-butynyloxy, 2-methyl-4- 30 haloalkenyl, C-C alkynyl, C-C alkoxyalkyl, C-C, bromo-3-butynyloxy, 1-methyl-4-chloro-3-butynyloxy and alkoxyimino, allyloxyimino or phenyl which may be option 1-methyl-4-bromo-3-butynyloxy. ally substituted with halogen, C-C alkyl or C-C alkoxy, For the substituents R' and R, examples of the C-C, with the proviso that when m is an integer of 2 to 4, R's are alkoxyalkyl are methoxymethyl, ethoxymethyl, the same or different, or two adjacent R's may be combined n-propyloxymethyl, isopropyloxymethyl, 2-methoxyethyl, 35 together at their terminal ends to form trimethylene or 1-methoxyethyl, 2-ethoxyethyl, 1-ethoxyethyl, 3-methoxy tetramethylene; D is oxygen; X's are the same or different n-propyl, 2-methoxy-n-propyl, 1-methoxy-n-propyl, and are independently chlorine or bromine; Y is oxygen, 2-methoxy-1-methylethyl and the like. NR, sulfur or C(R), wherein R is hydrogen or C-C, For the substituent R, examples of the C-C alkylthio alkyl and R's are the same or different and are indepen alkyl are methylthiomethyl, ethylthiomethyl, dently hydrogen or C-C alkyl; Z is nitrogen or CH, with n-propylthiomethyl, isopropylthiomethyl, the proviso that when Y is sulfur, Z is CH; P and Q are CH. 2-methylthioethyl, 1-methylthioethyl, 2-ethylthioethyl, More preferably, when Z is CH, R' is halogen, C-C, 1-ethylthioethyl, 3-methylthio-n-propyl, 2-methylthio-n- alkyl, trifluoromethyl, C-C haloalkoxy, C-C alkoxy, propyl, 1-methylthio-n-propyl, 2-methylthio-1-methylethyl C-C alkenyloxy, C-C haloalkenyloxy, cyclohexyl, and the like. 45 cyclopentyl, phenyl, phenoxy or pyridyloxy which may be For the substituent R', examples of the C-C cycloalkyl optionally substituted with halogen, C-C alkyl or are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the trifluoromethyl, with the proviso that when l is an integer of like. 2 or 3, R's are the same or different, or two adjacent R’s may be combined together at their terminal ends to form For the substituent R, examples of the C-C cycloalk 50 trimethylene, tetramethylene, methylenedioxy, ethylene enyl are 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, dioxy or CH=CH-CH=CH; and when Z is nitrogen, R' 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl and the is halogen, trifluoromethyl or nitro; R is halogen, C-C, like. alkyl, trifluoromethyl, C-C alkenyl, C-C haloalkenyl, For the substituent R', examples of the C-C cycloalky ethynyl, methoxymethyl, nitro, C-C alkoxyimino, ally loxy are cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, 55 loxyimino or phenyl, with the proviso that mis an integer of cyclohexyloxy and the like. 2 or 3, R's are the same or different, or two adjacent R's For the substituent R', examples of the C-C cycloalk may be combined together at their terminal ends to form enyloxy are 1-cyclopentenyloxy, 2-cyclopentenyloxy, tetramethylene; D is oxygen; X's are the same or different 3-cyclopentenyl oxy, 1 - cyclohexenyl oxy, and are independently chlorine or bromine; when Z is CH, 2-cyclohexenyloxy, 3-cyclohexenyloxy and the like. Y is oxygen, NR, sulfur or C(CH2)2 wherein R is as Examples of the C-C alkyl group which may be option defined above, and when Zis nitrogen, Y is oxygen or NH; ally present on the phenyl or phenoxy for the substituents R. P and Q are CH. and/or R are methyl, ethyl, n-propyl, isopropyl, n-butyl, Most preferably, when Z is CH, 1 is an integer 1 to 3 R' isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, is halogen, C-C haloalkyl, C-C alkyl, C-C alkoxy, neopentyl, tert-pentyl and the like. 65 C-C haloalkoxy, cyclohexyl, cyclopentyl, phenyl or When R' and R are independently phenyl, pyridyloxy, phenoxy, with the proviso that when l is an integer of 2 or benzyl or phenoxy. all of which may be optionally substi 3, R's the same or different, or two adjacent R's may be 5,698,702 5 6 combined together at their terminal ends to form different and are independently fluorine, chlorine, trifluo tetramethylene, methylenedioxy or CH=CH-CH=CH, romethyl or methyl. and R is halogen, trifluoromethyl, allyl or C. alkyl; and Alternatively, the novel intermediate compounds may be when Z is hitrogen, m is an integer of 1 or 2 R' is halogen of the formula: or trifluoromethyl, and R is halogen or methyl, with the proviso that when m is an integer of 1 or 2 R's are the same (R) or different, D is oxygen; X's are the same or different and are independently chlorine or bromine; when Zis CH, Y is oxygen, sulfur or C(CH), and when Z is nitrogen, Y is oxygen or NH; P and Q are CH. 10 The dihalopropene compounds of the present invention can be produced by the following production processes. wherein R' is halogen such as fluorine, chlorine, bromine or Production process A iodine, or trifluoromethyl; R is halogen, trifluoromethyl or The process A for producing the dihalopropene com C-C alkyl; and m is an integer of 1 to 4. pounds of the present invention comprises reacting a com 15 The above reaction is usually carried out in an inert pound of the formula II: solvent under the presence of a suitable base. Examples of the solvent to be used are ketones such as (R), (R) (ID acetone, methyl ethyl ketone and cyclohexanone, ethers such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane and C-C dialkyl ether (e.g., diethyl ether, diisopropyl ether), N,N-dimethylformamide, dimethylsulfoxide, hexameth ylphosphorous triamide, sulfolane, acetonitrile, nitromethane, halogenated hydrocarbons such as wherein R'R'', Y. D, Z, P, Q, l and m are each as defined dichloromethane, chloroform, 1,2-dichloroethane and above, with a compound of the formula III: 25 chlorobenzene, hydrocarbons such as toluene, benzene and L-CH-CH=CX (III) xylene, and water. These solvents can be used alone or in combination. wherein X is as defined above; and L is halogen such as Examples of the base to be used are hydroxides of alkali chlorine, bromine or iodine, mesyloxy or tosyloxy. metals or alkaline earth metals, such as lithium hydroxide, The raw material compound of the formula II is obtained 30 sodium hydroxide, potassium hydroxide and calcium by conventional production processes as depicted in the hydroxide; carbonates of alkali metals or alkaline earth Schemes below, and examples of the intermediates are also metals, such as lithium carbonate, sodium carbonate, potas listed therein. sium carbonate and calcium carbonate; hydrides of alkali The intermediate compounds include novel compounds of metals or alkaline earth metals, such as lithium hydride, the formula: 35 sodium hydride, potassium hydride and calcium hydride; C-C alkoxides of alkali metals, such as sodium (R) CF methoxide, sodium ethoxide and potassium tert-butoxide; 3 2 organic bases such as triethylamine and pyridine. If necessary, a catalyst such as an ammonium salt (e.g., trieth 4. O OH ylbenzylammonium chloride) may be added to the reaction system in an proportion of 0.01 to 1 mole to 1 mole of the ().s 6 compound II. The reaction temperature may be usually in the range of wherein R' is halogen, C-Cs alkyl, C-C haloalkyl, from -20° C. to the boiling point of a solvent used for the C-C alkoxy, C1-Chaloalkoxy, C-C alkenyloxy, C-C, 45 reaction or 150° C., more preferably from -5° C. to the haloalkenyloxy, C-C cycloalkyl, phenyl, pyridyloxy, phe boiling point of the solvent used for the reaction or 100° C. noxy or benzyl, the last four of which may be optionally The molarratio of the raw material and base to be used for substituted with halogen or C-C alkyl, C-C alkoxy, the reaction can optionally be set, but it is advantageous to C-C haloalkoxy or C-C haloalkxyl, with the proviso conduct the reaction using them in the equimolar ratio or in that when l is an integer of 2 to 5, the R's are the same or 50 a ratio similar thereto. different, and when l is an integer of 2 or 3, two adjacent After completion of the reaction, the reaction solution can R's may be combined together at their terminal ends to be subjected to ordinary post-treatments such as organic form trimethylene, tetramethylene, methylenedioxy, ethyl solvent extraction and/or concentration to isolate the desired enedioxy or CH=CH-CH=CH. compound. If necessary, the resultant compound can be The intermediate compounds further include novel com 55 purified by a method such as chromatography or recrystal pounds of the formula: lization. Production process B R1 R2 The process B for producing the dihalopropene compound of the present invention comprises reacting the compound of the formula II with an alcohol compound of the formula IV:

CF3 -CS-Be N OH HO-CH-CH=CX (IV) R2 wherein X is as defined above. 65 It is preferred that the above reaction is carried out in an wherein R' is halogen such as fluorine, chlorine, bromine or inert solvent under the presence of a suitable dehydrating iodine, or trifluoromethyl; and R and R' are the same or agent. 5,698,702 7 8 Examples of the dehydrating agent are active isomers having biological activity (e.g., (+)-isomer, dicyclohexylcarbodiimide, di(C-C alkyl)azodicarboxylate (e.g., diethylazodicarboxylate, (-)-isomer) and mixtures of these isomers in any ratio are diisopropylazodicarboxylate), tri(C-C alkyl)phosphine also included in the present invention. or triarylphosphine (e.g., triphenylphosphine, Some examples of the present dihalopropene compound trioctylphosphine, tributylphosphine) and the like. 5 of the present invention will be shown below; however, the Examples of the solvent to be used are hydrocarbons such present invention is not limited thereto. as benzene, xylene and toluene; ethers such as diethyl ether, The compound of the following formulae VT-1 to VT-6 are diisopropyl ether, tetrahydrofuran and dioxane; halogenated shown in Table 1. hydrocarbons such as carbon tetrachloride, dichloromethane, chlorobenzene and dichlorobenzene. O The reaction temperature may be usually in the range of TABLE 1. from -20°C. to 200°C. or the boiling point of a solventused (R) CHCHCH3 for the reaction. 3 2 The molar ratio of the raw material and dehydrating agent to be used for the reaction can optionally be set, but it is 15 4. O OCHCH=CC (VT-1 advantageous to conduct the reaction using them in the equimolar ratio or in a ratio similar thereto. s s After completion of the reaction, the reaction solution can be subjected to ordinary post-treatments such as organic (R) CH2CHCH solvent extraction and/or concentration to isolate the desired 20 compound. If necessary, the resultant compound can be purified by a method such as chromatography or recrystal O OCHCH=CBr (VD-2 lization. Production process C (when D is an oxygen atom in the dihalopropene compound of the present invention): (R) CHCH3)2 The production process C for producing the dihalopro 25 pene compound of the present invention comprises reacting an aldehyde compound of the formula V: O OCHCHECC (VI)-3

(R) (R) (V) 30 (Ri), CHCH3) Cy--(y-o- ()- O -C- OCHCHECBr (WD-4 wherein R,R,Y,Z, P, Q, landmare each as defined above, 35 (R) CF with carbon tetrachloride or carbon tetrabromide. It is preferred that the above reaction is carried out in an inert solvent under the presence of a suitable trialkylphos phine or triarylphosphine, if necessary, under the presence of metallic zinc. Examples of the solvent to be used are hydrocarbons such (R), CF as benzene, xylene and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chlorobenzene (excluding carbon tetrabromide and car 45 bon tetrachloride). The reaction temperature may be usually in the range of from -30° C. to the boiling point of a solvent used for the (R), (R'), reaction or 150° C. 2-F 2,3,4-Cla Examples of the (C-C trialkyl)phosphine or tri 50 3.F 2,3,6-Cl arylphosphine are triphenylphosphine, trioctylphosphine 4-F 2,4,6-Cl 2,3-F 2,3,5-Cl and the like. It is preferred that metallic zinc optionally used 3,4-F 2,4,5-Cl is in a dust form. 2,6-F 2,3,4,5,6-Cl The molar ratio of the raw material and reagent to be used 2,4-F2 2-Bt for the reaction can optionally be chosen. The proportion of 55 2,5-F 3-Br 3,5-F 4-Br carbon tetrabromide (tetrachloride), trialkylphosphine or 2,3,4-F 3,5-Bra triarylphosphine and metallic zinc is 2 moles, 2 or 4 moles 2,3,6-F 2,4-Bra and 2 moles, respectively, to 1 mole of the aldehyde com 2,3,5-Fs. 2 pound of the formula V. 2,4,5-F 3. 2,3,5,6F 4 After completion of the reaction, the reaction solution can 2,3,4,5,6-Fs 2-F, 4-Cl be subjected to ordinary post-treatments such as organic 2-Cl 3-F, 4-Cl solvent extraction and/or concentration to isolate the desired 3-Cl 3-Cl, 4-F compound. If necessary, the resultant compound can be 4-Cl 2-Br, 4-F 2,3-Cl 2-F, 4-Br purified by a method such as chromatography or recrystal 2,6-Cl 2-Br, 5-F lization. 65 3,5-Cl 2-Br, 4-Cl If the dihalopropene compound of the present invention 24-Cl 2-Cl, 4-F contains an asymmetric atom, the corresponding optically

5,698,702 29 30

TABLE 7-continued TABLE 8-continued 3-OCHCCH) 3-Cl, 5-CF 4-OCHCCH)3-OCF, 3,5-(CF)3-Br, 5-CF 5 - O (R) 4-OCF 3,5-(CF), 6-Cl 3-OCHCF O 2-Cl, 4-CF O - OCHCH=CCl2 (XIII-9 5-CF, 10 The compounds of the formulae XIII-1 to 16 are shown in O (R) Table 8. TABLE 8 O OCHCH-CBr2 (XIII)-10 15 (R) 3 2 O (R) o- OCH-CH=CC, (XIID-1 ( 20 O O OCHCHCCl (XIII-11 s s (R) ( O (R) O OCHCH=CBr2 (XIII)-2 25 O O OCHCH=CBr2 (XIII)-12 (R)

30 O OCHCHCCl2 (XIII-3 (R)

(R) 35 -)--a CXIII)-13 O OCHCH=CBr, CXIII)-4 (R) (R2) K) -)- (XIII)-14 O OCHCHECC (XIII)-5 (R) 45 (R2) ( ) O OCH2CHCC CXIII-15 -(). OCHCHECBr2 (XIII)-6 50 K)( ) -(y-o-(R) (XIII)-16 (R) 55 (R) (R) OCHCHECC CXI-7 2-CF 2-CHF -(ty 2-CHCHCH 2,5-Cl 2-CHCCH) 3,5-Cl 60 2-Cl trimethylene at positions 2 and 3 2-Br tetramethylene at positions 2 and 3 (R2) The position of R is numbered as shown in the formula XIII-1

OCHCHECBr2 (XIII-8 65 -Cy The compounds of the formulae XTV-1 to 16 are shown in Table 9.

5,698,702 39 40

TABLE 12-continued TABLE 13-continued

(R) C (R), Cl ("y- Y -Cy- S-CHCH-CBr2 (XVID-4 5 (y-o-y- (XVIII)-7 e N

(R'), Y 10 (R) C1 4-OCHCCH) CCH). 3-OCHCCH), CCH) 4-OCH CCH) (y- OCHCH=CBr (XVIII)-8 3-OCH CCH) 4-OCHCCH) CHCCH) is v- N 3-OCHCCH) CHCH) 4-OCH CHCH) (R) B 3-OCH CHCH.) The compounds of the formulae XVIII-1 to 36 are shown 2O / W O OCHCHECC (XVIII-9 in Table 13. N

TABLE 13 (R) B

C 25 OCHCHECBr2 (XVIII)-10 OCHCHECC (XVIII-1 e N -) (R) C1 Cy OCHCH=CC1, CKVIII)-11 OCHCHECBr (XVIII-2 35 -C - -)C (R) C1 B OCHCHECBr2 (XVIID-12 OCHCHECC (XVIII-3 Cl

Br (R) C 45 B OCH2CHECC (XVIID-13 (y- OCHCHECBr2 (XVIEE)-4 -) 50 -C-C (R) C1

55 OCHCHECBr (XVIII)-14 OCHCHCCl (XVIII)-5 -C-Cl B C 60 (R H3 (y. OCHCHECBr2 (XVIII)-6 // OCHCHECCl2 (XVIII-15 -)-B 65 -C H S. 5,698,702 41 42

TABLE 13-continued TABLE 13-continued (R) CH3 (R), ( y O OCH2CHCBr2 (XVIII)-16 ( y ... O / OCHCHECCl2 (XVIII-25 -CH3 S O (R) CF. (R), C / OCHCHECBr2 (XVED-26 OCHCHECC (XVIII)-17 y Cy -y 15 -C) B r (R) CH3

C. (R) OCH2CHECC (XVIII)-27 (y- OCHCHECBr (XVIII)-18 e N (R) CH 25 (R), (y- OCHCHECBr2 (XVIII)-28 ( y OCH2CHECC CXVIII)-19 -)- (R) CH3

(R) OCHCHECCl (XVIII-29 35

OCH2CHECBr (y- B r e N C (R): C H

(R), C l C s OCHCHECBr2 (XVIII)-30 OCH2CHECC (XVIII)-21 Cy - S 45 (R) -()-crisB-()-V 50 OCHCHECCl (XVIII)-31 (y- -y- OCHCH ECBra CXVIII)-22 yy P. N re/s/ (R) (R) CF 55 OCHCHECBr (XVIII)-32 (y- OCHCHCCl (XVIII-23 e N e N -)- (R) CH3 (R) CF OCH2CHECCl (XVIII)-33 OCHCHECBr: 65 CH

5,698,702 61 62 The intermediate compound II of the present invention can be produced, for example, by the methods of schemes 1 to 10.

Scheme 1. Y is O. NR or S; L is a halogen; L is methyl or benzyl; and other ls are the same as above. (R) (R) (R) (R) / V / W Base(e.g., NaOH H-L1 OL 2-CuorNaH, cuprous K2CO3) halogenide Ge. / W Y.1. / \ OL2 P. Z. Pa Q (e.g., CuC) e Z. PE Q

(R) (R) Deprotection / V / V Same condition as above E.Eacoli, OL2 P. Z. P Q (R), (R) (R) R). (yer / \ -Cyr-y- P (Y1 is not NR3.)

Scheme 2. L is hydrogen or acetyl; and other symbols are the same as defined above ("y-r-,(R) -(y-(R) (y-o-y-(R) (R)

Base Cu or cuproushalogenide Base Cu or cuprous halogenide Cy--(y-(R) (R) ("y-r-y-(R), (R)

(R), (R) (R) (R)

all Z. Pa Q 2) EtOCSSK e Z. Pa Q 5,698,702 63 64

Scheme 3. The ls are the same as defined above. (R): (R) (R)t (R) / \ CHL + H. / W OL2 -Friedel-Crafts reaction e (y- ?y OL2 P. Z. P = Q Z. P = Q (R) (R)2 Grignards / \ / E-Z o

CHCI + BrMg OL2 E. Z. P = Q (R) (R) (R) (R) / \ LiAlH4/AICH3 or CH / W OH clemmensen reduction

P = Q (R'CHMgBr or (RCHPPrsCl ii) H3Ot (R) (R) (R)

-continued Scheme 4. Scheme 4. q is an integer of 1 or 2, and other symbols are the same as above. 35 q' is an integer of 1 or 2, and other symbols are the same as above. (R) (R)

Oxidant (e.g., H2O2-AcOH) 45

(R) (R2)

("y--(y. 50 P. Z. o 5,698,702 65 66

Scheme 5. The bols are the same as defined above, (R), (R) R4 / \ g-oh - H / \ OH as Z R4. P = Q Mineral acid or Lewis acid (R), (R) R4 /V f / W OH a Z. R. FQ (R) (R) - R4 Lewis acid / V f-l -- H / \ OH P. Z. R4 Pat Q

-continued Scheme 6. 25 Scheme 6. Y is a Y other than NH; D is oxygen or NH; R and Rare Y is a Y other than NH; D is oxygen or NH; R and R' are the same or different and are independently hydrogen, chlorine, the same or different and are independently hydrogen, chlorine, bromine or iodine, with the proviso that they are not simul usly bromine or iodine, with the proviso that they are not simultaneously hydrogen; and others are the same as defined above. hydrogen; and others are the same as defined above, 30 (R)-2 (R) (R) R21 Chlorination / W bromination or / V Y2 DH iodination G 35 Y2 DH

e 2. e A R2 (R) R21 40 / V Y2 DH Scheme 7. (R) Z. R22 Methylation 45 Y2 OH-9 allylation G (R) (R)-1 e Z. +1) (R) R21 Y2 DH. Same as above G

e Z. 50 / \ Y2 OH

(R2 e Z. (R) "ia, R22 / \ 55 (R)11 (R)-1 Y2 DH Z. / \ Y2 oH Sane as above G

60 2. (R)R1 (R)-2 (R) (R)- R21

/ \ 1. SameSusave as above e / \ Z. 65 Z. 5,698,702 67 68 -continued -continued Scheme 7. as a Scheme 9. (R)11 (R)2 5 / V Y2 OH Same as above G RO Y2 OH

e Z.

( R1 ) (R2 )n-2 R2 10 / V Compounds shown in Scheme 6 and 7 Y2 OH e Z. R’ is a C-C alkyl, C-Chaloalkyl, R22 15 C-Cs alkenyl or C-Cs haloalkenyl; Y is a Y other than NH; R and R are the same or different and and Y isS theis S3 2S defined above.above are independently a hydrogen, methyl or an allyl, with the proviso that they are not simultaneously hydrogen; and others are the same as defined above The intermediate aldehyde compound of the formula V of *1) See, e.g., Tetrahedron Lett, 889 (1974). the present invention can be produced by the following scheme:

Scheme 8. (R) (R)-12. (R)1. (R)-1CHNORS

a Z. Formylation (e.g., (CH3)2NCHO POCl3) HNOR or its salt (L: hydrogen atom) (R) (R)- CHO R) 2. "CHOR, (R) 'ichor.

Z. 3 E.R. Z. Deprotection- V- Z. Carbon addition (e.g. PPh3-CCl or CBra-Zn)

1. 2 (R) (R)-1CH=C(R6) (R)-1 (R)-1 CH=C(R6) (R) (R)- E CH (y- Y OL (y- Y OH / V Y OH Z. Deprotection V Elimination 1 \le z (e.g. n-Buli) L. rer or "y-y; it is an alkyl of C-C; R is chlorine or bromine; and other symbols are the same as defined above,

55 Schene 10. Scheme 9. R1) (R) - 5,698,702 69 70 -continued Coleoptera (beetles) Scheme 10. Diabrotica (corn rootworms) such as Diabrotica virgifera and Diabrotica undecimpunctata, Scarabaeidae such as (R), (R2) Anomala cuprea and Anomala rufocuprea, Curculionidae 5 (snout beetles) such as Sitophilus zeanais (grain weevils), Lissorhoptrus oryzophilus, Hypera postica, and Calosobru chus chinesis, Neatus ventralis (darkling beetles) such as Tenebrio molitor and Tribolium castianeum, Chrysomelidae (leaf beetles) such as Aulacophora femoralis, and Phyllot o conc. HC/AcOH) reta striolata, Anobiidae (death-watch beetles), Epilachna O spp. such as Epilachna vigintioctopunctata, Lyctidae Aldehyde compound of the formula W (powder-post beetles), Bostrychidae (lesser grain borers), Cerambycidae, etc.; The symbols are the same as defined above. Blattaria (cockroaches) Blattella germanica (croton bugs), Periplanetafiuliginosa, The intermediate compound represented by the formula 15 Periplaneta americana, Periplaneta brunnea, Blatta III and the alcohol compound represented by the formula IV orientalis, etc.; can be produced by the scheme 11 below or commercially Thysanoptera (thrips) available. Thrips palmi, Thrips tabaci, Thrips hawaiiensis, etc.; Hymenoptera Scheme 11. 20 Formicidae (ants), Vespa (hornets), Bethylidae (bethylid N-chlorosuccinimide, wasps), Tenthredinoidae (sawflies) such as Athalia rosae N-bromosuccinimide, japonensis (cabbage sawfly), etc.; xc=CHCH4-chlorine or bromine e Orthoptera Gryllotalpha (mole crickets), Acridoidea (grasshoppers), 1) Sodium acetate 25 etc.; 2)KCO3/MeOH Siphonaptera (fleas) Purex irritans, etc.; Mesyl chloride or tosylchloride Anoplura (sucking louses) XCeCCHOH Base XC-CCHL Pediculus humanus capitis, Phthirus pubis, etc.; 30 Isoptera (termites) L is chlorine or bromine, L is mesyloxy or tosyloxy, Reticuliterimes speratus, Coptotermes formosanus, etc.; and X is the same as defined above. Mites The dihalopropene compound of the present invention is Tetranychidae (spider mites) such as Tetranychus effective for controlling noxious insects, mites and nema cinnabarinus, Tetranychus urticae, Tetranychus kanzawaii, todes listed below: 35 Panonychus citri and Panonychus ulmi, Eriophyidae such as Hemiptera w Aculops pelekassi and Calacarus carinatus, Tarsonemidae Delphacidae (planthoppers) such as Laodelphax such as Polyphagotarisonemus latus, Tenuipalpidae, striatellus, Nilaparvata lugens and Sogatellafurcifera; Dei Tuckerellidae, Ixodidae (ticks) such as Boophilus microplus, tocephalidae (leafhoppers) such as Nephotettix cincticeps Acaridae, Pyroglyphidae, Cheyletidae, Dermanyssidae, etc.; and Nephotettix virescens, Aphidiidae (aphids), Pentatomi 40 Moreover, the dihalopropene compounds of the present dae (stink bugs), Aleyrodidae, Coccoidea (scale insects), invention are also effective for controlling various insects Tingidae (lacebugs), Psyllidae (jumping plant-lices), etc.; with increased resistance to commercially available insec Lepidoptera ticides. Pyralidae such as Chilo suppressalis, Cnaphalocrocis For the practical use of the dihalopropene compound of medinalis, Ostrinia nubilalis, Parapediasia teterrella, 45 the present invention as an active ingredient of insecticides, Notarcha derogata and Plodia interpunctella, Noctuidae acaricide or nematocides, it may be used as such; however, (owlet moths) such as Spodoptera litura, Pseudaletia the dihalopropene compound of the present invention is separata, Mamestra brassicae, Agrotis ipsilon, Heliothis usually formulated into oil sprays, emulsifiable moths, Helicoverpa moths, Pieridae such as Pieris rapae concentrates, wettable powders, flowable concentrates such crucivora, Tortricidae (bell moths) such as Grapholita 50 as water suspensions or emulsions, granules, dusts, aerosols, molesta and Cydia pomonella, Carposina niponensis, Lyo heating fumigants such as combustible fumigant, chemical netiidae (leaf mining moths), Euproctis and Lymantria fumigant and porous ceramics fumigant, ULV formulations (gypsy) moths, Yponomeutidae such as Plutella xylostella, and poison baits. These formulations are usually prepared by Gelechiidae such as Pectinophora gossypiella, Arctiidae mixing the dihalopropene compound of the present inven Such as Hyphantria cunea, Tinea translucens, Tineola 55 tion with a solid carrier, a liquid career, a gaseous carrier or bisselliella, etc.; bait, and a surfactant and any other auxiliary for formulation Diptera are added thereto, if necessary. These formulations usually Culex (house mosquitos) such as Culex pipiens pallens contain the dihalopropene compound of the present inven and Cules tritaeniorhynchus, Aedes such as Aedes aibopic tion as an active ingredient in an mount of 0.01% to 95% by tus and Aedes aegypti, Anophelinae such as Anophelies 60 weight. sinensis, Chironomidae (midges), Muscidae such as Musca Examples of the solid carrier to be used for the formula domestica (house fly) and Muscina stabulans, Caliphoridae tion are fine powder or granules of clays Such as kaolin clay, (blow flies), Sarcophagidae (flesh flies), Anthomyiidae such diatomaceous earth, synthetic hydrated silicon oxide, ben as Delia Platura and Delia antigua, Trypetidae (fruit flies), tonite and acid clay; talc, ceramics, inorganic minerals such Drosophilidae (wine flies), Psychodidae (moth flies), Taban 65 as sericite, quartz, sulfur, active carbon, calcium carbonate idae (deer flies), Simuliidae (black flies), Stomoxyinae, and hydrated silica; and chemical fertilizers such as ammo Agromyzidae (leaf miner flies) etc.; nium sulfate, ammonium phosphate, ammonium nitrate, 5,698,702 71 72 urea and ammonium chloride. Examples of the liquid carrier colloid are casein, gelatin, gums, cellulose ethers and poly are water; alcohols such as methanol and ethanol; ketones vinyl alcohol. Examples of the thixotropy-giving compound such as acetone and methylethyl ketone; aromatic hydrocar are bentonite, aluminum magnesium silicate, xanthan gum bons such as benzene, toluene, xylene, ethylbenzene and or polyacrylic acid. methylnaphthalene; aliphatic hydrocarbons such as hexane, The formulation thus obtained is used as such or after cyclohexane, kerosine and gas oil; esters such as ethyl dilution with water. The formulations of the present inven acetate and butyl acetate; nitriles such as acetonitrile and tion may be used together with otherinsecticides, acaricides, isobutyronitrile; ethers such as diisopropyl ether and diox nematocides, bactericides, herbicides, plant growth ane; acid amides such as N,N-dimethylformamide and N,N- regulators, synergists, fertilizers and/or soil conditioners dimethylacetamide; halogenated hydrocarbons such as O under non-mixing conditions or pre-mixing conditions. dichloromethane, trichloroethane and carbon tetrachloride; Examples of the insecticide, acaricide and/or nematocide dimethyl sulfoxide; and vegetable oils such as soybean oil to be used are organophosphorous compounds such as and cottonseed oil. Examples of the gaseous carrier or Fenitrothion (O,O-dimethyl O-(3-methyl-4-nitrophenyl) propellant are CFCs (chlorofluorocarbons), butane gas, LPG phosphorothionatel, Fenthion (O,O-dimethyl O-(3-methyl (liquefied petroleum gas), diethyl ether and carbon dioxide. 15 4-methylthiophenyl)phosphorothionate, Diazinon Examples of the surfactant are alkyl sulfates, alkyl (Dimpy late) IO, O-diethyl-O-2-isopropyl-6- sulfonates, alkyl arylsulfonates, alkyl aryl ethers, polyeth methylpyrimidin-4-ylphosphorothioate), Chlorpyriphos ylene glycols, polyethylene glycol ethers, polyhydric alco O,O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate), hol derivatives and sugar alcohol derivatives. Acephate O.S.-dimethyl acetylphosphoramidothioate), Examples of the auxiliary for the formulation, such as a Methidachion (DMTP) S-2,3-dihydro-5-methoxy-2-oxo-1, fixing agent or a dispersing agent, are casein, gelatin, 3,4-thia diazol-3-ylmethyl O, O polysaccharides such as starch, gum arabic, cellulose deriva dimethylphosphorothiolothionate), Disulfoton O,O-diethyl tives and alginic acid, lignin derivatives, bentonite, sugars S-2-ethylthioethyl phosphorothiolothionate, Dichlorvos and synthetic water-soluble polymers such as polyvinyl (DDVP) (2,2-dichlorovinyl dimethyl phosphate), Sulprofos alcohol, polyvinyl pyrrollidone and polyacrylic acid. 25 (O-ethyl O-4-methylthiophenyl S-propyl Examples of the stabilizer are PAP (isopropyl acid phosphorodithioate, Cyanophos IO-4-cyanophenyl-O,O- phosphate), BHT (2,6-di-t-butyl-4-methylphenol), BHA dimethylphosphorothioate), Dioxabenzofos 2-methoxy (mixture of 2-t-butyl-4-methoxyphenol and 3-t-butyl-4- 4H-1,3,2-benzodioxaphosphorin-2-sulfide), Dimethoate methoxyphenol), vegetable oils, mineral oils, surfactants, IO,O-dimethyl S-(N-methyl-carbamoylmethyl) fatty acids and esters of fatty acids. 30 phosphoro dithioate), Phentho ate ethyl Examples of the base material to be used in the combus 2-dimethoxyphosphinothiaylthiophenylacetate), Malathion tible fumigant are exothermic agents such as nitrates, 1,2-bis(ethoxylcarbonyl)-ethyl O,O-dimethyl nitrites, guanidine salts, potassium chlorate, nitrocellulose, phosphorothiolothionate, Trichlorfon (Metrifonate) ethylcellulose or wood powder; pyrolytic stimulating agents dimethyl 2,2,2-trichloro-1-hydroxyethyl phosphonatel, such as alkaline metal salts, alkaline earth metal salts, 35 AZinphos-methyl S-(3,4-dihydro-4-oxo-1,2,3- dichromates or chromates; oxygen sources such as potas benzotriazine-3-yl methyl) dimethyl sium nitrates; combustion assistants such as melamine or phosphorothiolothionate, Monocrotophos dimethyl-(E)-1- wheat starch; bulk fillers such as diatomaceous earth; and methyl-2-(methylcarbamoyl) vinyl phospahteland Ethion binding agents such as synthetic glue. IO, O, O', O'- tetraethyl-S, S'-methylene bis Examples of the base material to be used in the chemical (phosphorothiolothionate). fumigant are exothermic agents such as alkaline metal Other examples are carbamate compounds such as BPMC sulfides, polysulfides, hydrogensulfides, hydrated salts or 2-sec-butylphenyl methyl carbamate), Benfuracarb ethyl calcium oxide; catalytic agents such as carbonaceous N-(2,3-dihydro-2,2-dimethyl benzofuran-7-yloxycarbonyl substances, iron carbide or active clay; organic foaming (methyl)aminothio)-N-isopropyl-3-alaninate, Propoxur agents such aS a zodicarbon amide, 45 (PHC) 2-isopropoxyphenyl N-methyl carbamate), Carbo benzene sulfonyl hydrazide, N,N'- sulfan 2,3-dihydro-2,2-dimethyl-7-benzoblfuranyl dinitrosopentamethylenetetramine, polystyrene or polyure N-dibutylaminothio-N-methyl carbamate), Carbaril thane; and fillers such as natural and synthetic fibers. 1-naphthyl N-methylcarbamatel, Methomyl S-methyl-N-( Examples of the base material to be used in the poison (methylcarbamoyl)oxy)thioacetoimidate, Ethiofencarb 2 baits are bait materials such as grain powder, purified 50 (ethylthiomethyl)phenyl methylcarbamate), Aldicarb vegetable oil, sulfur or crystalline cellulose; antioxidants 2-methyl-2-(methylthio)propion aldehyde such as dibutylhydroxytoluene or nordihydroguaiaretic acid; O-(methylcarbamoyl)oxime, Oxamyl N,N-dimethyl preservatives such as dehydroacetic acid; substances for 2-methylcarbamoyloxyimino-2-(methylthio)acetamide) and preventing erroneous eating, such as red pepper powder; Fenothiocarb IS-(4-phenoxybutyl)-N,N-dimethyl attractant flavors such as cheese flavor or onion flavor. 55 thiocarbamatel. The flowable concentrates such as water suspensions and Other examples are pyrethroid compounds such as emulsions are usually obtained by finely dispersing the Etofemprox 2-(4-ethoxyphenyl)-2-methylpropyl-3- dihalopropene compound of the present invention at a ratio phenoxybenzyl ether, Fenvalerate (RS)-o-cyano-3- of 1% to 75% in water containing a 0.5% to 15% dispersing phenoxybenzyl-(RS)-2-(4-chlorophenyl)-3- agent, a 0.1% to 10% suspension assistant (e.g., protective methylbutyrate), S-Fenvalerate (S)-o-cyano-3- colloid or a thixotropy-giving compound) and 0% to 10% phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate), additives (e.g., antifoamers, stabilizers, bactericides, rust Fenpropathrin (RS)-O-cyano-3-phenoxybenzyl 2,2,3,3- preventive agents, antimolds, developing agents, penetrating tetramethylcyclopropanecarboxylate), Cypermethrin (RS)- assistants and anti freezing agents). o-cyano-3-phenoxybenzyl (1RS,3RS)-3-(2,2-dichlorovinyl) The dihalopropene compound of the present invention 65 -2,2-dimethylcyclopropanecarboxylate, Permethrin may be dispersed in oil having substantially no solubility 3-phenoxybenzyl (1RS,3RS)-3-(2,2-dichlorovinyl)-2,2- thereof, to form oil suspensions. Examples of the protective dimethylcyclopropanecarboxylate), Cyhalothrin (RS)-O- 5,698,702 73 74 cyano-3-phenoxybenzyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3- and Pyrimidifen 5-chloro-N-(2-(4-(2-ethoxyethyl)-2,3- trifluoropropen-1-yl)-2,2-dimethylcyclopropane dimethylphenoxy)ethyl)-6-ethylpyrimidine-4-amine. carboxylatel, Deltamethrin (S)-O-cyano-3-phenoxybenzyl When the dihalopropene compound of the present inven ( 1 R, 3R)-3-(2, 2 - dibromo v in y1) - 2, 2 - tion is applied as an active ingredient of insecticides, nema dimethylcyclopropanecarboxylate, Cycloprothrin (RS)-0- tocides or acaricides for agricultural use, the amount for cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1-(4- application is usually 0.1 to 100 g or more, preferably 10 to ethoxyphenyl)cyclopropanecarboxylate, Fluvalinate 100g per 1000 m. When emulsifiable concentrates, wet O-cyano-3-phenoxybenzyl N-(2-chloro-O,O,O-trifluoro-p- table powders or flowable concentrates of the present com tolyl)-D-valinatel, Bifenthrin 2-methylbiphenyl-3- pound are diluted with water, the concentration for applica ylmethyl) (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoropropen 10 tion is 0.1 to 500 ppm. Granules and dusts are used without 1-yl)-2,2-dimethylcyclopropanecarboxylate, Acrinathrin any dilution. When the dihalopropene compound of the (S)-(0)-cyano-(3-phenoxyphenyl)methyl (1R)-(1c(S*).30, present invention is applied as an active ingredient of (Z))-2,2-dimethyl-3-(3-oxo-3-(2,2,2-trifluoro-1- insecticides or acaricides for domestic use, the emulsifiable (triflu or omethyl) eth oxy - 1 - prope nyl) concentrates, wettable powders, flowable concentrates and cyclopropane carboxylate, 2-methyl-2-(4- 15 emulsifiable concentrates are diluted, for example, with bromodifluoromethoxyphenyl)propyl (3-phenoxybenzyl) water to a concentration of 0.1 to 500 ppm. Oil sprays, ether, Traromethrin (S)-O-cyano-3-phenoxylbenzyl (1R, aerosols, fumigants, ULV agents and poisonous baits are 3S)-3-((1"RS) (1", 1,2',2'-tetrabromoethyl))-2,2- used without any dilution, dimethylcyclopropanecarboxylate and Silafluofen The amount and concentration for application may be 4-ethoxylphenyl(3-(4-fluoro-3-phenoxyphenyl)propyl) 20 changed optionally according to the type of the formulation dimethylsilanel. used, time, place and method of application, the type of Other examples are thiadiazine derivatives such as Bupro noxious organisms and the damage. fezin 2-t-butylimino-3-isopropyl-5-phenyl-1,3,5- The present invention will be further illustrated by the thiadiazin-4-one, nitroimidazolidine derivatives such as following Examples, Formulation Examples and Biological Imidacloprid (1-(6-chloro-3-pyridylmethyl)-N- 25 Test Examples, which are not to be construed to limit nitroimidazolidin-2-ylidenamine, Nereistoxin derivatives thereof. such as Cartap S.S'-(2-dimethylaminotrimethylene) The following will describe some examples of the diha bisthiocarbamatel, Thiocyclam N,N-dimethyl-1,2,3- lopropene compound of the present invention. trithian-5-ylamine and Bensultap S, S-2- EXAMPLE 1. dimethylaminotrimethylene di(benzenethiosulfonate), 30 N-cyanoamidine derivatives such as N-cyano-N'-methyl-N'- Production of compound 208 by production process A (6-chloro-3-pyridylmethyl)acetoamidine, chlorinated To a mixture of 93 mg of 3,5-dichloro-4-(3-chloro-5- hydrocarbons such as Endosulfan 6,7,8,9,10,10 trifluoromethyl-2-pyridyloxy)phenol, 40 mg of potassium hexachloro-1.5.5a,6,99a-hexahydro-6.9-methanobenzoe carbonate and 10 ml of N,N-dimethylformamide, a solution 2,4,3-dioxathiepin 3-oxide, Y-BHC 1,2,3,4,5,6- 35 prepared by dissolving 42 mg of 1,1,3-trichloro-1-propene hexachlorocyclohexane), 1,1-bis(chlorophenyl)-2,2,2- in 3 ml of N,N-dimethylformamide was added dropwise at trichloroethanol, benzoylphenylurea compounds such as room temperature with stirring. After stirring at room tem Chlorofuazuron 1-(3,5-dichloro-4-(3-chloro-5- perature for 5 hours, the reaction solution was poured into trifluoromethylpyrid-2-yloxy) phenyl)-3-(2,6- ice-water, and extracted twice with 40 ml of diethyl ether. difluorobenzoyl)urea, Tefiubenzuron I-(3,5-dichloro-2,4- Then, the ether layers were combined, washed with water. difluorophenyl)-3-(2,6-difluorobenzoyl)ureal and dried over anhydrous magnesium sulfate and concentrated to Fulphenoxron 1-(4-(2-chloro-4-trifluoromethylphenoxy)- give a crude product. This crude product was subjected to 2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea, formamidine silica gel chromatography to give 96 mg of 3,5-dichloro-4- derivatives such as Amitraz N'-(2,4-dimethylphenyl)-N-((2, (3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro 4 - dimethyl phenyl)imino) methyl)-N- 45 2-propenyloxy)benzene, yield 79%; m.p., 97.8° C. methylmethanimidamide) and Chlordimeform N'-(4- chloro-2-methylphenyl)-N,N-dimethylmethanimidamide), EXAMPLE 2 thiourea derivatives such as Diafenthiuron N-(2,6- Production of compound 1 by production process A diisopropyl-4-phenoxyphenyl)-N'-t-butylthioureal; Fipro To a mixture of 0.65 g of 3-ethyl-4-(4- nyl (5-amino-1-(2,6-dichloro-O,0,0-trifluoro-p-tolyl)-4- 50 isopropoxyphenoxy)phenol, 0.35 g of potassium carbonate trifluoromethylsulfinylpyrazole-3-carbonitrite, and 10 ml of N,N-dimethylformamide, a solution prepared Bromopropylate isopropyl 4,4'-dibromobenzilate, Tetradi by dissolving 0.73g of 1,1,3-tribromo-1-propene in 5 ml of fon (2,4,4,5-tetrachlorodiphenyl sulfone, Quinomethionate N,N-dimethylformamide was added dropwise at room tem 6-methyl-2-oxo-1,3-dithiolo-(4,5-b)quinoxaline), Proparg perature with stirring. After stirring at room temperature for ite 2-(4-(1,1-dimethylethyl)phenoxy)cyclohexyl-2- 55 12 hours, the reaction solution was poured into ice-water, propynyl sulfite, Fenbutatin oxide bis(tris(2-methyl-2- and extracted twice with 50 ml of diethyl ether. Then, the phenylpropyl)tin)oxide), Hexythiazox (4RS,5RS)-5-(4- ether layers were combined, washed with water, dried over chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3- anhydrous magnesium sulfate and then concentrated to give thiazolidine-3-carboxamide, Chlofentezine 3,6-bis(2- a crude product. This crude product was subjected to silica chlorophenyl)-1,2,4,5-tetrazine), Pyridathioben 2-t-butyl gel chromatography to give 0.80 g of 3-ethyl-4-(4- 5-(4-t-butylbenzylthio)-4-chloropyridazin-3 (2H)-one, isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy) Phenpyroxymate t-butyl (E)-4-((1,3-dimethyl-5- benzene, yield 71%: n' 1.5761. phenoxypyrazol-4-yl)methyleneaminooxymethyl) benzoate), Debphenpyrad N-4-t-butylbenzyl)-4-chloro-3- EXAMPLE 3 ethyl-1-methyl-5-pyrazol carboxamidel, polynactin 65 Production of compound 130 by production process A complexes including tetranactin, trinactin and dinactin; To a solution prepared by dissolving 0.44 g of Milbemectin, Avermectin, Ivermectin, Azadilactin AZAD 2-trifluoromethyl-4-(3-ethoxyphenoxy)phenol in 10 ml of 5,698,702 75 76 N,N-dimethylformamide, 0.062 g of sodium hydride (60% EXAMPLE 7 oil-based) was added with stirring under ice cooling. After Production of compound 196 by production process B 10 minutes, a solution prepared by dissolving 0.24 g of To a solution prepared by dissolving 0.55 g of 1,1,3-trichloro-1-propene in 5 ml of N,N- 2-trifluoromethyl-4-(4-ethoxyphenoxy)phenol, 0.40 g of dimethylformamide was added dropwise under ice cooling. 3,3-dibromoallyl alcohol and 0.49 g of triphenylphosphine After stirring at room temperature for 10 hours, the reaction in 10 ml of tetrahydrofuran, a solution prepared by dissolv solution was poured into ice-water, and extracted twice with ing 0.38 g of diisopropylazodicarboxylate in 5 ml of tet 50 ml of diethylether. Then, the ether layers were combined, rahydrofuran was added dropwise atroom temperature with washed with water, dried over anhydrous magnesium sulfate stirring. After stirring at room temperature for 12 hours, the and concentrated to give a crude product. This crude product 10 reaction solution was concentrated. Then, 20 ml of diethyl was subjected to silica gel chromatography to give 0.37 g of ether was added thereto, and the precipitate was filtered off. 2-trifluoromethyl-4-(3-ethoxyphenoxy)-1-(3,3-dichloro-2- The resulting filtrate was concentrated, and subjected to propenyloxy)benzene, yield 62%; n° 15369. Silica gel column chromatography to give 0.30 g of 2-trifluoromethyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2- EXAMPLE 4 15 propenyloxy)benzene, yield 32%; n' 1.5480. Production of compound 206 by production process A Example 8 To a mixture of 0.77 g of 2,5-dichloro-4-(3-bromo-5- Production of compound 68 by production process C trifluoromethyl-2-pyridyloxy)phenol, 0.29 g of potassium First, 0.38 g of zinc dust, 1.54 g of triphenylphosphine, carbonate and 20 ml of N,N-dimethylformamide, a solution 1.94 g of carbon tetrabromide and 20 ml of methylene prepared by dissolving 0.31 g of 1,1,3-trichloropropene in 5 chloride were charged into a reaction vessel, and stirred at ml of N,N-dimethylformamide was added dropwise at room room temperature. After 24 hours, a solution prepared by temperature with stirring. After stirring at room temperature dissolving 1.0 g of (2-bromo-4-(3-chlorophenoxy) phenoxy) for 10 hours, the reaction solution was poured into ice-water, 25 acetaldehyde in 5 ml of methylene chloride was added and extracted twice with 50 ml of ethyl acetate. Then, the dropwise to the solution with stirring. After stirring at room ethyl acetate layers were combined, washed with water, temperature for 6 hours, the reaction solution was concen dried over anhydrous magnesium sulfate and then concen trated to give a residue. This residue was subjected to silica trated to give a crude product. This crude product was gel column chromatography to give 0.48 g of 2-bromo-4- subjected to silica gel chromatography to give 0.81 g of (3-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy) 2,5-dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)- 30 benzene, yield 33%; n' 1.6282. 1-(3,3-dichloro-2-propenyloxy)benzene, yield 83%; m.p., 95.4° C. EXAMPLE 9 Production of compound 212 by production process A EXAMPLE 5 35 To a mixture of 0.56 g, of 3,5-dichloro-4-(3.5- bistrifluoromethyl-2-pyridyloxy)phenol, 0.22 g of potas Production of compound 273 by production process A sium carbonate and 20 ml of N,N-dimethylformamide, a To a mixture of 0.59 g of 2-bromo-4-(4-chlorophenylthio) solution prepared by dissolving 0.23g of 1,1,3-trichloro-1- phenol, 0.28 g of potassium carbonate and 20 ml of N.N- propene in 5 ml of N,N-dimethylformamide was added dimethylformamide, a solution prepared by dissolving 0.30 dropwise at room temperature with stirring. After stirring at g of 1,1,3-trichloropropene in 5 ml of N,N- room temperature for 7 hours, the reaction solution was dimethylformamide was added dropwise at room tempera poured into ice-water, and extracted twice with 50 ml of ture with stirring. After the mixture was stirred at room diethyl ether. Then, the ether layers were combined, washed temperature for 6 hours, the reaction solution was poured with water, dried over anhydrous magnesium sulfate and into ice-water, and extracted twice with 50 ml of diethyl 45 then concentrated to give a crude product. This crude ether. Then, the ether layers were combined, washed with product was subjected to silica gel chromatography to give water, dried over anhydrous magnesium sulfate and then 0.50 g of 3,5-dichloro-4-(3,5-bistrifluoromethyl-2- concentrated to give a crude product. This crude product was pyridyloxy)-2-(3,3-dichloro-2-propenyloxy)benzene, yield subjected to silica gel column chromatography to give 0.62 70%; m.p., 78.2° C. g of 2-bromo-4-(4-chlorophenylthio)-1-(3,3-dichloro-2- 50 EXAMPLE 10 propenyloxy)benzene, yield 78%; n° 16514. Production of compound 210 by production process A To a mixture of 0.83 g of 3,5-dichloro-4-(3-bromo-5- EXAMPLE 6 trifluoromethyl-2-pyridyloxy)phenol, 0.31 g of potassium 55 carbonate and 20 ml of N-dimethylformamide, a solution Production of compound 275 by production process B prepared by dissolving 0.33 g of 1,1,3-trichloro-1-propene To a solution prepared by dissolving 0.65 g of 2-bromo in 5 ml of N,N-dimethylformamide was added dropwise at 4-(1-methyl-1-(4-ethoxyphenyl)ethylphenol, 0.25g of 3,3- room temperature with stirring. After stirring at room tem dichloroallyl alcohol and 0.51 g of triphenylphosphine in 10 perature for 7 hours, the reaction solution was poured into ml of tetrahydrofuran, a solution prepared by dissolving 0.34 ice-water, and extracted twice with 50 mi of diethyl ether. g of diethylazodicarboxylate in 5 ml of tetrahydrofuran was Then, the ether layers were combined, washed with water, added dropwise at room temperature with stirring. After dried over anhydrous magnesium sulfate and then concen stirring at room temperature for 24 hours, the reaction trated to give a crude product. This crude product was solution was concentrated to give a residue. This residue was subjected to silica gel chromatography to give 0.79 g of subjected to silica gel chromatography to give 0.28 g of 65 3,5-dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)- 2-bromo-4-(1-methyl-1-(4-ethoxyphenyl)ethyl-1-(3.3- 2-(3,3-dichloro-2-propenyloxy)benzene, yield 75%; m.p., dichloro-2-propenyloxy)benzene, yield 32%; n' 1.5869. 90.7 C.

5,698,702 89 90 (325) 3,5-Dichloro-4-(5-nitro-2-pyridyloxy)-1-(3,3- (349) 3,5-Dichloro-4-(2,6-dichloro-4-trifluoromethyl) dibromo-2-propenyloxy)benzene, n' 16247 phenoxy-1-(3.3-dichloro-2-propenyloxy)benzene, n' (326) 2,6-Dichloro-4-(2,4-dinitrophenoxy)-1-(3,3- 15735 dichloro-2-propenyloxy)benzene, m.p., 74.9°C. (350) 3,5-Dichloro-4-(2-fluoro-4-nitrophenoxy)-1-(3.3- (327) 2-Bromo-4-(1-methyl-1-(3-chloro-5- dichloro-2-propenyloxy)benzene, m.p., 94.2°C. trifluoromethyl-2-pyridyloxy)phenyl)ethyl)-1-(3.3- (351) 3,5-Dichloro-4-(2-fluoro-4-nitrophenoxy)-1-(3.3- dichloro-2-propenyloxy)benzene, n° 1.5725 dibromo-2-propenyloxy)benzene, mp. 79.3° C. (328) 2-Bromo-4-(1-methyl-1-(3-chloro-5- (352) 3,5-Dichloro-4-(2-chloro-4-nitrophenoxy)-1-(3.3- trifluoromethyl-2-pyridyloxy)phenyl)ethyl)-1-(3,3- dichloro-2-propenyloxy)benzene, n' 1.6172 dibromo-2-propenyloxy)benzene, n° 1.5942 10 (353) 3,5-Dichloro-4-(2-chloro-4-nitrophenoxy)-1-(3.3- (329) 2-Bromo-4-(4-(3-chloro-5-trifluoromethyl-2- dibromo-2-propenyloxy)benzene, n° 1.6396 pyridyloxy)phenoxy)-1-(3.3-dichloro-2-propenyloxy) (354) 3,5-Dichloro-4-(6-chloro-3,5-bistrifluoromethyl-2- benzene, n° 1.5791 pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene, (330) 2-Bromo-4-(4-(3-chloro-5-trifluoromethyl-2- 15 m.p., 108.9°C. pyridyloxy)phenoxy)-1-(3,3-dibromo-2-propenyloxy) (355) 3,5-Dichloro-4-(2-nitro-4-trifluoromethylphenoxy) benzene, n° 1.5849 -1-(3,3-dichloro-2-propenyloxy)benzene, n' (331) 2-Methyl-5-chloro-4-(3-chloro-5-trifluoromethyl 15706 2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy) (356) 3,5-Dichloro-4-(2-nitro-4-trifluoromethylphenoxy) benzene, n. 18.5 1.5530 20 -1-(3,3-dibromo-2-propenyloxy)benzene, n' (332) 2-Methyl-5-chloro-4-(3-chloro-5-trifluoromethyl 1.5870 2-pyridyloxy)- 1-(3,3-dibromo-2-propenyloxy) (357) 3,5-Dichloro- 4-(2,4-dinitro -6- benzene, n. 15687 trifluoromethylphenoxy)-1-(3,3-dichloro-2- (333). 2-(1-Methyl-2-propenyl)-4-(4-isopropoxyphenoxy propenyloxy)benzene, n' 1.5778 -1-(3,3-dichloro-2-propenyloxy)benzene, ne’ (358) 3,5-Dichloro- 4-(2,4-dinitro -6- 5611. trifluoromethylphenoxy)-1-(3,3-dibromo-2- (334) 2-(1-Methyl-2-propenyl)-4-(4-isopropoxyphenoxy) propenyloxy)benzene, n' 1.588 -1-(3,3-dibromo-2-propenyloxy)benzene, n° (359) 3.5-Dichloro-4-(2-trifluoromethyl-4-nitrophenoxy) 15791 -1-(3.3-dichloro- 2-propenyloxy)benzene, n' (335) 3-Chloro-5-bromo-4-(3-chloro-5-trifluoromethyl 30 15757 2-pyridyloxy)-1-(3,3-dichloro-2-prope nyloxy) (360) 3,5-Dichloro-4-(2-trifluoromethyl-4-nitrophenoxy) benzene, m.p., 95.5° C. -1-(3,3-dibromo-2-propenyloxy)benzene, n' (336) 3-Chloro-5-bromo-4-(3-chloro-5-trifluoromethyl 15962 2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy) (361) 3.5-Dichloro-4-(2,4-bistrifluoromethylphenoxy)-1- benzene, m.p., 94.3° C. 35 (3,3-dichloro-2-propenyloxy)benzene, n' 1.5333 (337) 3.5-Dichloro-4-(4-cyanophenoxy)-1-(3,3-dichloro (362) 3,5-Dichloro-4-(2,4-dinitrophenoxy)-1-(3,3- 2-propenyloxy)benzene, m.p., 119.2° C. dibromo-2-propenyloxy)benzene, n° 1.6290 (338) 2,6-Dibromo-4-(3-chloro-5-trifluoromethyl-2- (363) 3-Methyl-4-(4-(2.2.2-trifluoroethoxy)phenoxy)-1- pyridylamino)-1-(3,3-dichloro-2-propenyloxy) (3.3-dichloro-2-propenyloxy)benzene, n° 1.5382 benzene, m.p., 117.1° C. (364) 3-Methyl-4-(4-nitrophenoxy)-1-(3,3-dichloro-2- (339) 3,5-Dichloro-4-(3-bromo-5-nitro-2-pyridyloxy)-1- propenyloxy)benzene, n° 1.6057 (3,3-dibromo-2-propenyloxy)benzene, m.p., 91.6° C. (365) 3.5-Dichloro-4-(4-acetamidophenoxy)-1-(3,3- (340) 3-Methyl-4-(3-methoxyphenoxy)-1-(3.3-dichloro dichloro-2-propenyloxy)benzene, glassy 2-propenyloxy)benzene, n° 1.5787 45 (366) 3,5-Dichloro- 4-(4- (341) 2-Isopropyl-5-chloro-4-(3-chloro-5- trifluoromethylacetamidophenoxy)-1-(3.3-dichloro-2- trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2- propenyloxy)benzene, n' 1.5708 propenyloxy)benzene, n° 1.5380 (367) 3,5-Dichloro- 4-(2,6-dichloro-4- (342) 2-Isopropyl-5-chloro- 4-(3-chloro-5- trifluoromethylphenoxy)-1-(3.3-dibromo-2-allyloxy) trifluoromethyl-2-pyridyloxy)-1-(3.3-dibromo-2- 50 benzene, n° 1.5878 propenyloxy)benzene, n° 1.5552 The following will describe some production examples of (343) 2-Bromo-4-(2-methyl-1-(4-ethoxyphenyl)propyl the intermediate compound of the formula II. 1-(3,3-dichloro-2-propenyloxy)benzene, n° 1.5791 EXAMPLE 11 (344) 2-Bromo-4-(2-methyl-1-(4-ethoxyphenyl)propyl 55 Production of intermediate compound 67 1-(3,3-dibromo-2-propenyloxy)benzene, m.p., 64.3°C. First, 1.07 g of hydroquinone monobenzyl ether and 500 (345) 2-Bromo-4-(2-methyl-1-(4-isopropoxyphenyl)) ml of carbon tetrachloride were charged into a reaction propyl-1-(3.3-dichloro2-propenyloxy)benzene, n” vessel, and a solution prepared by dissolving 1.01 g of 15694 t-butyl hypochlorite in' ml of carbon tetrachloride was (346) 2-Bromo-4-(2-methyl-1-(4-ethoxyphenyl)propyl slowly added dropwise with stirring under ice cooling. After 1-(3.3-dibromo-2-propenyloxy)benzene, n° 1,5820 24 hours, the reaction solution was poured into water and the (347) 2-Isopropyl-4-(2-methyl-4-(3,3-dichloro-2- organic layer (carbon tetrachloride) was separated. Then, the prope nyloxy))phenoxy-1-(3,3-dichloro-2- organic layer was washed with water, dried over anhydrous propenyloxy)benzene, n' 1.573 magnesium sulfate and concentrated to give a crude product. (348) 2-Isopropyl-4-(2-methyl-4-(3,3-dichloro-2- 65 This crude product was subjected to silica gel chromatog prope nyloxy))phenoxy-1-(3,3-dibromo-2- raphy to give 0.85 g of 2,6-dichloro-4-benzyloxyphenol propenyloxy)benzene, n' 1.6070 (yield, 59%). 5,698,702 91 92 Then, 0.85g of 2,6-dichloro-4-benzyloxyphenol, 0.48g tetra-n-butylammonium tribromide was added at room tem of potassium carbonate, 0.75 g of 2,3-dichloro-5- perature (about 20° C.) with stirring and the mixture was trifluoromethylpyridine and 10 ml of N,N- stirred at room temperature for additional 24 hours. To the dimethylformamide were charged into a reaction vessel, and reaction solution, 750 ml of a saturated sodium sulfite stirred at 85° to 90° C. for 3 hours. Then, the reaction solution was added, and the mixture was shaken vigorously solution was cooled to room temperature, poured into water to concentrate the chloroform layer. To the residue, 500 ml and extracted twice with 50 ml of diethyl ether. The ether of diethyl ether and 500 ml of 10% hydrochloric acid were layers were combined, washed with water, dried over anhy added, and the mixture was shaken vigorously. The ether drous magnesium sulfate and then concentrated to give a layer was dried over anhydrous magnesium sulfate and crude product. This crude product was subjected to silica gel concentrated to give 32 g of 4-bromo-2-isopropylphenol chromatography to give 1.39 g of 3,5-dichloro-4-(3-chloro (yield, 100%). 5-trifluoromethyl-2-pyridyloxy)-1-benzyloxybenzene, A mixture of 32 g of 4-bromo-2-isopropylphenol, 25.7g (yield, 98%). of benzyl bromide, 23 g of potassium carbonate and 300 m Then, 1.39 g of 3,5-dichloro-4-(3-chloro-5- of N,N-dimethylformamide was stirred at room temperature trifluoromethyl-2-pyridyloxy)-1-benzyloxybenzene, and 20 15 for 24 hours. The reaction solution was poured into ice ml of methylene chloride were charged into a reaction water, acidified by adding 10% hydrochloric acid and then vessel, and a solution of boron tribromide (1.63 g) in extracted with 500 ml of diethyl ether. Then, the ether layer methylene chloride (10 ml) was added dropwise with stir was washed with a saturated saline solution, dried over ring under ice cooling (-10° C. to 0°C). After stirring for anhydrous magnesium sulfate and concentrated. The residue one hour under ice cooling, the mixture was poured into was subjected to silica gel column chromatography to give 10% hydrochloric acid and extracted twice with 50 ml of 30 g of 4-bromo-2-isopropylphenyl benzyl ether (yield, methylene chloride. Then, the organic layers were 65%). combined, washed with water, dried over anhydrous mag A mixture of 10 g of 4-bromo-2-isopropylphenyl benzyl nesium sulfate and concentrated to give a crude product. ether, 4.7 g of 4-ethoxyphenol, 4.7 g of potassium carbonate, This crude product was subjected to silica gel column 25 0.30 g of copper powder, 0.30 g of cuprous iodide and 30 ml chromatography to give 1.03 g of 3,5-dichloro-4-(3-chloro of pyridine was stirred at 130° C. to 140° C. for 24 hours. 5-trifluoromethyl-2-pyridyloxy)phenol (yield, 93%), m.p., The reaction solution was cooled to room temperature, 152.6° C. poured into ice-water and then acidified by adding 10% hydrochloric acid. The solution was extracted with 100 ml of EXAMPLE 12 30 diethyl ether, washed in turn with 10% hydrochloric acid, an Production of intermediate compound 63 aqueous 10% sodium hydroxide solution and a saturated To a solution prepared by dissolving 2.8 g of hydro saline solution, dried over anhydrous magnesium sulfate and quinone in 20 ml of N,N-dimethylformamide, 1.39 g of then concentrated. The residue was subjected to silica gel sodium hydride (60% oil-based) was added, slowly, with column chromatography to give 4.4 g of 4-(4- stirring under ice cooling. After completion of the genera 35 ethoxyphenoxy)-2-isopropylpheny benzyl ether (yield, tion of hydrogen gas from the reaction solution, a solution 37%). prepared by dissolving 5 g of 2,3-dichloro-5- Then, 4.4 g of 4-(4-ethoxyphenoxy)-2-isopropylphenyl trifluoromethylpyridine in 10 ml of N,N- benzyl ether and 100 ml of ethyl acetate were charged into dimethylformamide was added dropwise. After stirring at a reaction vessel, and air in the vessel was replaced with room temperature for 3 hours, the reaction solution was nitrogen. Then, 0.50 g of 5% palladium-carbon was added, poured into ice-water, and extracted twice with 200 ml of and nitrogen in the vessel was replaced with hydrogen, diethyl ether. Then, the ether layers were combined, washed followed by vigorous stirring at room temperature for 24 with water, dried over anhydrous magnesium sulfate and hours. After hydrogen in the vessel was replaced with then concentrated to give a crude product. This crude nitrogen, the reaction vessel was filtered with Celite, and the product was subjected to silica gel chromatography to give 45 filtrate was concentrated. The residue was subjected to silica 2.88 g of 4-(3-chloro-5-trifluoromethyl-2-pyridyloxy) gel chromatography to give 3.1 g of 2-isopropyl-4-(4- phenol (yield, 43%). ethoxyphenoxy)phenol (yield, 93%). To a solution prepared by dissolving the resulting 2.88 g n° 15612 of 4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol in 50 "H-NMR (CDCl/TMS) 8 (ppm): 1.22 (6H, d), 1.41 (3H, 300 ml of chloroform, 4.80 g of tetra-n-butylammonium t), 3.13–3.22 (1H, m), 4.01 (2H, q), 4.69 (1H, s), 6.62–6.93 tribromide was slowly added with stirring under room (7H, m) temperature. After 12 hours, the reaction solution was concentrated, and the residue was extracted twice with 100 EXAMPLE 14 ml of diethyl ether. Then, the ether layers were combined, 55 Production of intermediate compound 87 washed with water, dried over anhydrous magnesium sulfate First, 7.44 g of 4,4'-bispropylidenebiphenol, 4.63 g of and then concentrated to give a crude product. This crude 2-bromopropane, 4.53 g of Potassium carbonate and 50 ml product was subjected to silica gel chromatography to give of N.N dimethylformide were charged into a reaction vessel, 2.53 g of 2-bromo-4-(3-chloro-5-trifiuoromethyl-2- and the mixture was stirred at an oil bath temperature of 80° pyridyloxy)phenol (yield, 69%). C. to 90° C. for 6 hours. The reaction solution was poured "H-NMR (CDCl/TMS) 8 (ppm): 5.54 (1H, br), 7.06(3H, into water and extracted three times with 30 ml of ethyl brs), 7.33 (1H, d), 7.97 (1H, d), 8.27 (1H, d) acetate. Then, the ethyl acetate layers were combined, washed with water, dried over anhydrous magnesium sulfate EXAMPLE 1.3 and concentrated to give a crude product. This crude product Production of intermediate compound 5 65 was subjected to silica gel chromatography to give 3.89 g of First, 20.4 g of 2-isopropylphenol and 750 ml of chloro 4-(1-(4-isopropyloxyphenyl)-1-methylethyl)phenol (yield, form were charged into a reaction vessel, and 80 g of 44%). 5,698,702 93 94 To a solution of 4-(1-(4-isopropyloxyphenyl)-1- EXAMPLE 16 methylethyl)phenol (0.51 g) in carbon tetrachloriode (1.3 ml), a solution prepared by dissolving 0.23g of tert-butyl Production of intermediate compound 29 hypochlorite in 0.5 ml of carbon tetrachloride was added First, 41.33 g of 2-trifluoromethylphenol and 1800 ml of dropwise with stirring under ice cooling. After 30 minutes, chloroform were charged into a reaction vessel, and 129.16 an ice bath was removed, and the mixture was stirred at g of tetra-n-butylammonium tribromide was slowly added at room temperature for 30 minutes. The reaction solution was room temperature over about one hour with stirring. After poured into water and extracted three times with 5 ml of stirring at room temperature for 72 hours, the reaction carbon tetrachloride. Then, the carbon tetrachloride layers solution was concentrated. Then, 500 ml of 10% hydrochlo were combined, washed with water, dried over anhydrous 10 ric acid was added to the resultant residue, and the mixture magnesium sulfate and then concentrated to give a crude was extracted four times with 200 ml of diethyl ether. The product. This crude product was subjected to silica gel ether layers were combined, washed with water, dried over column chromatography to give 0.49 g of 4-(1-(4- anhydrous magnesium sulfate and then concentrated to give isopropyloxyphenyl)-1-methylethyl)-2-chlorophenol (yield, 49.5g of 4-bromo-2-trifluoromethylphenol as a crude prod 85%). 15 uct (yield, 81%). in 15557; Then, 8.47 g of 4-bromo-2-trifluoromethylphenol, 5.34g "H-NMR (CDC/TMS) 8 (ppm): 1.33 (6H, d), 1.62 (6H, of potassium carbonate, 4.49 g of benzyl chloride and 100 s), 5.43 (1H, s), 6.78 (2H, d), 6.89 (1H, d), 7.02 (1H, dd), ml of N,N-dimethylformamide were charged into a reaction 7.11 (2H, d), 7.18 (1H, d) vessel, and stirred under ice cooling. After 24 hours, the EXAMPLE 1.5 20 reaction solution was poured into ice-water and extracted Production of intermediate compound 23 three times with 50 ml of diethyl ether. The ether layers were A mixture of 6.3 g of 4-isopropoxyphenol, 10.5 g of combined, washed with an aqueous 10% sodium hydroxide 4-bromophenyl benzyl ether, 8.3 g of potassium carbonate, solution, dried over anhydrous magnesium sulfate and then 0.5g of copper powder, 0.5g of cuprous chloride and 3.5g concentrated to give a crude product. This crude product was of pyridine was stirred at 130° C. to 140° C. for 24 hours. 25 subjected to silica gel chromatography to give 9.38 g of The reaction solution was cooled to room temperature, 4-bromo-2-trifluoromethyl-1-benzyloxybenzene, (yield, pound into water and then acidified by adding 10% hydro 81%). chloric acid. The solution was extracted with 100 ml of Then, 5.10 g of 4-bromo-2-trifiuoromethyl-1- diethyl ether, washed in turn with 10% hydrochloric acid, an benzyloxybenzene, 2.34 g of p-ethoxyphenol, 2.13 g of aqueous 10% sodium hydroxide solution and a saturated 30 potassium carbonate, 100 mg of copper and 200 mg of saline solution, dried over anhydrous magnesium sulfate and cuprous chloride were charged into a reaction vessel, and then concentrated. The crude product was subjected to silica stirred at 130° C. to 140° C. for 5 hours. The reaction gel column chromatography to give 4.3 g of 4-(4- solution was cooled to room temperature, poured into ice isopropyloxy)phenylbenzyl ether (yield, 32%). water and then acidified by adding 10% hydrochloric acid. Then, 4.3 g of 4-(4-isopropyloxy)phenylbenzyl ether and 35 The solution was extracted twice with 100 ml of diethyl 100 ml of ethyl acetate were charged into a reaction vessel, ether. Then, the ether layers were combined, washed with and air in the vessel was replaced with nitrogen. Then, 0.50 water, dried over anhydrous magnesium sulfate and concen g of 10% palladium-carbon was added, and nitrogen in the trated to give a crude product. This crude product was vessel was replaced with hydrogen, followed by vigorous subjected to silica gel chromatography to give 2.50 g of stirring at room temperature for 24 hours. After hydrogen in 2- triflu or omethyl-4-(4-ethoxyphen oxy)-1- the vessel was replaced with nitrogen, the reaction vessel benzyloxybenzene, (yield, 41%). was filtered with Celite, and the filtrate was concentrated. Then, 2.50 g of 2-trifluoromethyl-4-(4-ethoxyphenoxy)- The residue was subjected to silica gel column chromatog 1-benzyloxybenzene, 100 ml of ethyl acetate and 0.50 g of raphy to give 2.8 g of 4-(4-isopropoxyphenoxy)phenol 10% palladium-carbon were charged into a reaction vessel, (yield, 89%). and air in the vessel was replaced with nitrogen. Then, To a mixture of 1.23 g of 4-(4-isopropoxyphenoxy) nitrogen was replaced with hydrogen at room temperature phenol, 1.4 g of potassium carbonate and 10 ml of N,N- with stirring. After stirring at room temperature for 24 hours, dimethylformamide 0.65 ml of allyl bromide was added the reaction solution was filtered, and the filtrate was con dropwise at room temperature with stirring. After 24 centrated to give a crude product. This crude product was minutes, the reaction solution was poured into water, and 50 subjected to silica gel chromatography to give 1.75 g of acidified by adding 10% hydrochloric acid. The solution was 2-trifluoro-4-(4-ethoxyphenoxy)phenol (yield, 91%). extracted with 50 ml of diethyl ether, washed in turn with 10% hydrochloric acid, an aqueous 10% sodium hydroxide n° 15322 and a saturated saline solution, dried over anhydrous mag Other examples of the intermediate compound of the nesium sulfate and then concentrated. The residue was 55 formula II will be described below. Subjected to silica gel column chromatography to give 0.98 1) 2-n-Propyl-4-(4-ethoxyphenoxy)phenol g of 4-(4-isopropoxyphenoxy)phenyl allyl ether (yield, "H-NMR (CDC/TMS) 8 (ppm): 0.96 (3H, t), 1.41 (3H, 69%). t), 1.55-1.67 (2H, m), 2.53 (2H, t), 4.01 (2H, q), 4.62 (1H, Then, 0.98 g of 4-(4-isopropoxyphenoxy)phenyl allyl s), 6.70-6.93 (7H, m) ether was heated at 190° C. to 200° C. for 6 hours with 2) 2-Isopropyl-4-(2-chloro-4-ethoxyphenoxy)phenol stirring. The reaction product was cooled to room tempera "H-NMR (CDC/TMS) 6 (ppm): 1.23 (6H, d), 1.41 (3H, ture and then subjected to silica gel column chromatography t), 3.12-3.22 (1H, m), 4.01 (2H, q), 4.62 (1H, s), 6.56-6.99 to give 0.85 g of 2-allyl-4-(4-isopropoxyphenoxyphenol (6H, m) (yield, 87%). 3) 2-Ethyl-4-(4-ethoxyphenoxy)phenol "H-NMR (CDCl/TMS) 8 (ppm): 132 (6H, d), 335-3.38 65 "H-NMR (CDCl/TMS) 8 (ppm): 1.20 (3H, t), 1.39 (3H, (2H, m), 4.41-4.51 (1H, m), 4.77 (1H, s), 5.11-5.20 (2H, m), t), 2.58 (2H, q), 3.99 (2H, q), 4.54 (1H, s), 6.57-7.08 (7H, 5.97-6.07 (1H, m), 6.73-6.91 (7H, m) m)

5,698,702 99 100 "H-NMR (CDC/TMS) 8 (ppm): 1.41 (3H, t), 4.07 (2H, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of q), 6.04 (1H, brs), 6.89 (2H, d, J-9.7 Hz), 7.27 (2H, d, J-9.6 bentonite and 55 parts of clay, and stirred sufficiently. Then, Hz), 7.48 (2H, s) a suitable amount of water is added to the mixture which is 81) 4-(4-Methoxyphenylthio)-2-(trifluoromethyl)phenol further stirred, granulated with a granulated and then air "H-NMR (CDC/TMS) 8 (ppm): 3.78 (3H, s), 5.10 (1H, dried to give a 5% granular for each compound. brs), 6.84 (1H, d, J=9.2 Hz), 6.88 (2H, d, J-8.8 Hz), 7.29 (1H, dd, J=2.2, 9.2 Hz), 7.32 (2H, d, J-8.8 Hz), 7.47 (1H, d, FORMULATION EXAMPLE 4 J=2.2 Hz) Dusts 82) 4-(4-Isopropyloxyphenylthio)-2-bromophenol 10 One part of each of the compounds 1 to 367 separately 1H-NMR (CDC1/TMS) 8 (ppm): 1.33 (6H, d),453 (1H, dissolved in a suitable amount of acetone is mixed with 5 sep), 5.45 (1H, s), 6.83 (2H, d), 6.92 (1H, s), 7.16 (1H, dd), parts of synthetic hydrated silicon hydroxide fine powder, 7.29 (2H, d), 7.40 (1H, d) 0.3 parts of PAP and 93.7 parts of clay. Then, the mixture 83) 4-(1-(4-Isopropyloxyphenyl)-1-methylethyl)-2- was stirred with a mixer and acetone is removed to give 1% bromophenol dusts for each compound. "H-NMR (CDC/TMS) 8 (ppm): 1.33 (6H, d), 1.61 (6H, 15 s), 4.51 (1H, sep), 6.82 (2H, d), 6.91 (1H, d), 7.05 (1H, dd), FORMULATION EXAMPLE 5 7.11 (2H, d), 7.32 (1H, d) 84) 4-(4-Isopropyloxyphenyl)-methyl-2-bromophenol Flowables "H-NMR (CDC/TMS) 8 (ppm): 1.33 (6H, d), 3.82 (2H, Twenty parts of each of the compounds 1 to 367 are s), 4.52 (1H, sep), 5.42 (1H, s), 6.83 (2H, d), 6.94 (1H, d), separately mixed with 1.5 parts of sorbitan trioleate and 28.5 7.05 (1H, dd), 7.07 (2H, d), 7.27 (1H,d) parts of an aqueous solution containing 2 parts of polyvinyl 85) 4-(1-(4-Isopropyloxyphenyl)-ethyl)-2-bromophenol alcohol, and the mixture is pulverized into fine particles "H-NMR (CDC/TMS) 8 (ppm): 1.36 (6H, d), 1.60 (3H, having a particle size of not more than 3 m with a sand d), 4.05 (1H, q), 4.56 (1H, sep), 5.46 (1H, brs), 6.85 (2H, d), 25 grinder. Each of the mixture was mixed with 40 parts of an 6.96 (1H, d), 7.10 (1H, dd), 7.13 (2H, d), 7.33 (1H, d) aqueous solution containing 0.05 parts of Xanthan gum and 86) 4-(N-(3-chloro-5-(trifluoromethyl)-2-pyridyl)amino)- 0.1 parts of aluminum magnesium silicate, and then mixed 2,5-dichlorophenol with 10 parts of propylene glycol to give 20% water-based "H-NMR (CDC/TMS) 8 (ppm): 5.75 (1H, brs), 7.12 suspensions for each compound. (1H, s), 7.62 (1H, s), 7.80 (1H, s), 8.40 (1H, s), 8.52 (1H, s) 30 FORMULATION EXAMPLE 6 87) 4-(1-(4-Isopropoxyphenyl)-1-methylethyl)-2- chlorophenol Oil solutions "H-NMR (CDCl/TMS) 8 (ppm): 1.33 (6H. s), 1.62 (6H, First, 0.1 parts of each of the compounds 1 to 367 are s), 5.43 (1H, s), 6.78 (2H, d). 6.89 (1H, d), 7.02 (1H, dd), separately dissolved in 5 parts of xylene and 5 parts of 7.11 (2H, d), 7.18 (1H, d) 35 trichloroethane. Then, the solution was mixed with 89.8 88) 2-Trifluoromethyl-4-(3-trifluoromethylphenoxy) parts of deodorized kerosine to give 0.1% oil solutions for phenol each compound. 89) 2-Trifluoromethyl-4-(3-phenoxyphenoxy)phenol n? 15679 FORMULATION EXAMPLE 7 The following will describe Formulation Examples. In Oil-based aerosol these Formulation Examples, "parts” are by weight unless First, 0.1 parts of each of the compounds 1 to 367, 0.2 otherwise stated. parts of tetramethrin, 0.1 parts of d-phenothrin, 10 parts of FORMULATION EXAMPLE 1. trichloroethane are dissolved in 59.6 parts of deodorized 45 kerosine, and an aerozol vessel is filled with the solution. Emulsifiable concentrates Then, the vessel is equipped with a valve, through which 30 Ten parts of each of the compounds 1 to 367 are sepa parts of a propellant (liquefied petroleum gas) are charged rately dissolved in 35 parts of xylene and 35 parts of under pressure to give an oil-based aerosol of each com dimethylformamide. Each of the resultant mixtures is mixed pound. with 14 parts of polyoxyethylene styrylphenyl ether and 6 50 parts of calcium dodecylbenzenesulfonate, and stirred suf FORMULATION EXAMPLE 8 ficiently to give 10% emulsifiable concentrates for each compound. Water-based aerosol An aerosol vessel is filled with 50 parts of pure water and FORMULATON EXAMPLE 2 55 a mixture of 0.2 parts of each of the compounds 1 to 367, 0.2 Wettable powders parts of d-allethrin, 0.2 parts of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosine and 1 part of an Twenty parts of each of the compounds 1 to 367 are emulsifier ATMOS 300 (registered trade mark by Atlas separately added to a mixture of 4 parts of sodium lauryl Chemical Co.). Then, the vessel is equipped with a valve, sulfate, 2 parts of calcium lignin sulfonate, 20 parts of through which 40 parts of a propellant (liquefied petroleum synthetic hydrated silicon hydroxide fine powder and 54 60 parts of diatomaceous earth, and stirred with a mixer to give gas) are charged under pressure to give a water-based 20% wettable powders for each compound. aerosol of each compound. FORMULATION EXAMPLE 3 FORMULATION EXAMPLE 9 Granular 65 Mosquito-coil To 5 parts of each of the compounds 1 to 367 are added First, 0.3 g of each of the compounds 1 to 367 and 0.3g 5 parts of synthetic hydrated silicon hydroxide fine powder, of d-allethrin are dissolved in 20 ml of acetone, and the 5,698,702 101 102 solution is mixed uniformly with 99.4 g of a carrier for artificial diet for Spodoptera litura, which was prepared in a mosquito-coil (prepared by mixing Tabu powder, dregs polyethylene cup having a diameter of 11 cm in advance, powder and wood flour in the ratio of 4:3:3) with stirring. was impregnated with 2 ml of a 200-folded diluted solution Then, 120 ml of water is added to the mixture, which is of the emulsion (500 ppm) in water. Ten fourth instar larvae kneaded sufficiently, molded and dried to give a mosquito 5 of Spodoptera litura were set free in the cup. After six days, coil of each compound. the survival of larvae was examined to determine the mor tality in duplicate. FORMULATION EXAMPLE 10 As a result, it was found that the compounds 1-3, 6-14, Electric mosquito-mat 16-21, 23-28, 31-33, 36-45, 47-62, 64-69, 76-78, 80, 84, First, 0.4 g of each of the compounds 1 to 367, 0.4 parts 10 86-90, 92-97, 103-114, 116-122, 124, 125, 127-133, 135, of d-allethrin and 0.4 g of pipenyl butoxide are separately 136, 138-185, 189-216, 218-224, 226-233,236, 237, dissolved in acetone to give 10 ml of a solution. A substrate 239-242, 244-246, 248-253, 262, 265, 266, 267, 271, for electric mat having a size of 2.5 cmx1.5 cmx0.3 cm in 273-280, 292-294, 297-303, 305, 309-313, 316, 317, thickness (prepared by forming a fibrillated mixture of 319-321,323,329-336,338,339,347, 349-356, 359-361, cotton inter and pulp into a sheet) is impregnated uniformly 15 363, 366 and 367 exhibited the mortality of not less than with 0.5 ml of the solution to give an electric mosquito-mat 80%. In contrast, the compounds A and B exhibited the of each compound. mortality of 0%. FORMULATION EXAMPLE 11 BIOLOGICAL TEST EXAMPLE 2 Heating smoke formulation Test against Tetranychus urticae Koch Ten Female imagines of Tetranychus urticae Koch per First, 100 mg of each of the compounds 1 to 367 is one leaf were allowed to parasitize to a poring bean har separately dissolved in a suitable amount of acetone. Then, vested for 7 days after seeding (primary leaf stage), which a porous ceramic plate having a size of 4.0 cmx4.0 cmx1.2 was placed in a greenhouse maintained at 25 C. After 6 cm in thickness is impregnated with the resultant solution to 25 days, 15 ml of a chemical solution (containing 500 ppm of give a heating smoke formulation of each compound. an active ingredient), which was prepared by diluting an FORMULATON EXAMPLE 12 emulsion of the test compound obtained according to For mulation Example 1 with water, was sprayed over a pot on Poison baits 30 a turntable. At the same time, 2 ml of the same solution was First, 10 mg of each of the compounds 1 to 367 is direnched in the soil. After 8 days, the degree of damage of separately dissolved in 0.5 ml of acetone, and the solution is the respective plants caused by Tetranychus urticae Koch mixed uniformly with 5 g of solid bait powder (Breeding was examined. The activity was evaluated according to the Solid Feed Powder CE-2, trade name by Japan Clea Co., criteria: Ltd.). Then, acetone is removed to give a 0.2% poison bait 35 -: Damage is scarcely observed. of each compound. +: Damage is slightly observed. The following Biological Test Examples will illustrate -H: Damage is observed at the same level as in the that the dihalopropene compounds of the present invention non-treated field. are useful as an active ingredient of insecticides/acaricides. As a result, it was found that the compounds 1, 5–9, 12, In these Biological Test Examples, the dihalopropene com 13, 19, 21-28, 31-38, 41-49, 51,53,55-63, 65-73, 75, 76, pounds of the present invention are designated by the 79-86, 89-91, 93, 97, 100-108, 110, 115, 126-130, corresponding numbers described above and the compounds 136-151,155-158, 163-165, 169, 179-181, 183, 188, 190, used for comparison are designated by the corresponding 191, 193, 196, 197, 200, 202, 210-213, 215, 236-239, symbols in Table 22. 242-244, 247,250, 252-255, 257-262, 265, 266, 268, 45 270-274,276, 277,279, 280, 291-296,303, 305,309, 310, TABLE 22 318,319,323,329-331, 333, 340-343, 348 and 363 were Symbol evaluated as "-" or "+". In the contrast, the compounds A of com and B were evaluated as '-'. pound Chemical Structure Remarks What is claimed is: 50 1. An intermediate compound of the formula: A. Compound dis (y- O -(y- OCHCHECC closed in the Japanese Pat (R) CF entLaid-open 3 PublicationNo. 48-86835/1973 55 Compound dis B ()- CHO -(y- OCH-CH=CC, closed in the s s Japanese Pat ent aid-open whereinl is an integer of 1 to 5; R' is halogen, C-C alkyl, PublicationNo. trifluoromethyl, C-C alkoxy, C-C, C-C alkenyloxy, 49-1526/1974 C-C haloalkenyloxy, C-C cycloalkyl, phenyl, pyridyloxy, phenoxy or benzyl, the last four of which may BIOLOGICAL TEST EXAMPLE 1. be optionally substituted with halogen, C-C alkyl, C-C, alkoxy, C-C haloalkyl or C-C haloalkoxy, with the Insecticidal test against Spodoptera litura 65 proviso that when 1 is an integer of 2 to 5, R's are the same An emulsion was prepared from the test compound or different, and when l is an integer of 1 to 3, two adjacent according to Formulation Example 1. Then, 13 g of an R's may be combined together at their terminal ends to 5,698,702 103 104 form trimethylene, tetramethylene, methylenedioxy, ethyl 4. An intermediate compound according to claim 1, which enedioxy or CH=CH-CH=CH. is 2-trifluoromethyl-4-(4-cyclohexylphenoxy)phenol. 2. An intermediate compound of the formula: 5. An intermediate compound according to claim 1, which is 2-trifluoromethyl-4-(2,6-dichloro-4- R (R) 5 trifluoromethylphenoxy)phenol. 6. An intermediate compound according to claim 1, which is 2-trifluoromethyl-4-(5,6,7,8-tetrahydro-2-naphthyloxy) CF / W NH OH phenol. P. N. 7. A compound which is 3,5-dichloro-4-(3.5- O bistrifluoromethyl-2-pyridyloxy)phenol. wherein R' is halogen or trifluoromethyl; R's are the same 8. An intermediate compound according to claim2, which or different and are independently halogen, trifluoromethyl is 2,6-dichloro-4-(3-chloro-5-trifluoromethyl-2- or C-C alkyl; and m is an integer of 1 to 4. pyridylamino)phenol. 3. An intermediate compound according to claim.1, which is 2-trifluoromethyl-4-(4-isopropoxyphenoxy)phenol.