Indian Patents
Title of Invention

DICHLORO SUBSTITUTED PROPENYLOXY BENZENE DERIVATIVES
Abstract The present invention relates to a compound of the general formula: wherein R<sup>2</sup> and R<sup>3</sup> are independently halogen, C<sub>1</sub>-C<sub>3</sub> alkyl or C<sub>1</sub>-C<sub>3</sub> haloalkyl, R<sup>7</sup> is hydrogen or C<sub>1</sub>-C<sub>3</sub> alkyl, R<sup>10</sup> and R<sup>11</sup> are independently hydrogen, C<sub>1</sub>-C<sub>3</sub> alkyl or trifluoromethyl, X's are independently chlorine or bromine, L<sup>1</sup> is hydroxy, halogen, methanesulfonyloxy or p-toluenesulfonyloxy, and e is an integer of 2 to 4.
Full Text This invention relates to dichlcro substituted
prcpenylcxy benzene derivatives. These compounds are novel intermediates in the preparation of dihaloprcpene compounds claimed in the parent application no.963/MAS/95.
Background Art
As disclosed in JP-A 48-86835/1973 and JP-A 49-1526/1974, for example, it is well known that some kinds of propene compounds can be used as an active ingredient of insecticides.
In view of their insecticidal/acaricidal activity, it cannot always be said that these compounds are satisfactorily active for the control of noxious insects, mites and ticks.
Disclosure of Invention
The present inventors have intensively studied to find a compound having excellent insecticidal/acaricidal activity. Asa result, they have found that particular dihalo-propene compounds have satisfactory insecticidal/acaricidal activity for the control of noxious insects, mites and ticks, thereby completing the present invention.
That is, the present invention provides a dihalopropene compound (hereinafter referred to as the present compound) of the general formula:








trifluoromethyl, X's are independently chlorine or bromine, L1 is hydroxy, halogen, methanesulfonyloxy or p-toluenesulfonyloxy, and e is an integer of 2 to 4; and particularly, a compound wherein R , R and R11 are all hydrogen, and e is 2 or 3;


wherein R2 and R are independently halogen, C1C1 alkyl or C1-C3 haloalkyl, R is hydrogen or CyC1 alkyl, R10 and R11 are independently hydrogen, C1-C3 alkyl or trifluoromethyl, R20 is halogen, C1-C3 alkoxy, trifluoromethyl or Q-C3 haloalkoxy, /is an integer of 0 to 5, and e is an integer of 1 to 4; and particularly, a compound wherein B is oxygen; a compound wherein R and R are independently halogen or CpC3 alkyl,

R7, R10 and R11 are all hydrogen, e is 1 to 4, and B is oxygen, S(O)t or NR13 wherein R13 is hydrogen, acetyl or C1-C3 alkyl, and t is an integer of 0 to 2.
Detailed Description of the Invention
The variables in the above formulae for the present compounds and their intermediates can take the following specific examples.
Examples of the halogen atom represented by R2, R3, R4, R5, R6, R8, R9 or R12 or present in R9 are fluorine, chlorine, bromine or iodine.
Examples of the Cj-Cio alkyl group represented by R1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, n-heptyl, isohexyl, n-octyl, n-nonyl, n-decyl, 3-n-pentyl, 2-ethylbutyl, 1-methylpentyl, 1-ethylbutyl, 3-methylpentyl, 1,3-dimethylbutyl, 1-methyl-heptyl and 1-methyloctyl.
Examples of the C\-C^ alkyl group present in R or R , or represented by R
19
or R , are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
Examples of the CrC3 alkyl group represented by R2, R3, R5, R6, R7, R10, R11, R13, R14, R15 or R16 are methyl, ethyl, n-propyl and isopropyl.
Examples of the CpCg alkyl group represented by R are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, 1-ethylpropyl, n-hexyl, isohexyl, 2-ethylbutyl, 1-methylpentyl, 1-ethylbutyl, 3-methylpentyl, 1,3-dimethylbutyl, n-heptyl, n-octyl and 1-methylheptyl.
Examples of the C1-C5 haloalkyl group represented by R are trifluoro-methyl, difluoromethyl, bromodifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-dichloroethyl, 2-bromo-1,1,2,2-tetrafluoroethyl, 1,1,2,2,-tetrafluoroethyl, 2-chloro-l,l,2-trifluoroethyl, 2-bro-mo-l,l,2-trifluoroethyl, 2,2,2-trichloroethyl, 2,2,2-tribromoethyl, 3-chloropropyl, 3-bro-mopropyl, 3-fluoropropyl, 3-iodopropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoro-propyl, 1,1,2,3,3,3-hexafluoropropyl, 2-chloropropyl, 1-chloro-l-methylethyl, 1-bromo-1-methylethyl, 2-fluoro-l-(fluoromethyl)ethyl, 2-chloro-l-(chloromethyl)ethyl, 2-bromo-

















dioxane and dialkyl (e.g., C1-C4) ether (e.g., diethyl ether, diisopropyl ether); N,N-di-methylformamide, dimethylsulfoxide, hexamethylphophoric triamide, sulforane, aceto-nitrile, nitromethane; halogenated hydrocarbons 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.
Examples of the base which can be used are hydroxides of alkali metals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals, such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate; hydrides of alkali metals or alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alkoxides (e.g., C1-C4), such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; and organic bases such as triethylamine and pyridine. If necessary, catalysts such as ammonium salts (e.g., triethylbenzylammonium chloride) may be added to the reaction system at a ratio of 0.01 to 1 mole per mole of the compound of the general formula [VI].
The reaction temperature is usually set within the range of -20°C to 150°C or the boiling point of a solvent used in the reaction, preferably -5°C to 100°C or the boiling point of a solvent used in the reaction.
The molar ratio of the starting materials and bases 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.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic solvent extraction and concentration, and the desired compound of the present invention can be isolated. Further, purification can be carried out, if necessary, by an ordinary technique such as chromatography, distillation or recrystallization.

(Production Process B for the present compounds wherein Y is oxygen) In this process, a compound of the general formula [VI] is reacted with an alcohol compound of the general formula:
HO-CH2CH=CX2 [VIII]
wherein X is as defined above.
The reaction is preferably effected in an inert solvent, if necessary, in the presence of a suitable dehydrating agent.
Examples of the dehydrating agent which can be used are dicyclohexyl-carbodiimide, and dialkyl (e.g., C1-C4) azodicarboxylates (e.g., diethylazodicarboxylate, diisopropylazodicarboxylate)-trialkyl (e.g., CJ-C20) phosphine or triarylphosphine (e.g., triphenylphosphine, trioctylphosphine, tributylphosphine).
Examples of the solvent which can be used are hydrocarbons such as benzene, xylene and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydro-furan and dioxane; and halogenated hydrocarbons such as carbon tetrachloride, dichloro-methane, chlorobenzene and dichlorobenzene.
The reaction temperature is usually set within the range of -20°C to 200°C or the boiling point of a solvent used in the reaction.
The molar ratio of the starting 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.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic solvent extraction and concentration, and the desired compound of the present invention can be isolated. Further, purification can be carried out by an ordinary technique such as chromatography, distillation or recrystallization.
(Production Process C for the present compounds wherein Y is oxygen)
In this process, an aldehyde compound of the general formula:


The reaction is preferably effected in an inert solvent in the presence of a suitable trialkylphosphine or triarylphosphine, and if necessary, in the presence of metal zinc.
Examples of the solvent which can be used are hydrocarbons such as benzene, xylene and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydro-furan and dioxane; and halogenated hydrocarbons (exclusive of carbon tetrabromide and carbon tetrachloride) such as dichloromethane, 1,2-dichloroethane and chlorobenzene.
The reaction temperature is usually set within the range of -30°C to 150°C or the boiling point of a solvent used in the reaction.
Examples of the trialkyl (e.g., C1-C20) phosphine or triarylphosphine are triphenylphosphine and trioctylphosphine. The metal zinc which is used, if necessary, is preferably in dust form.
The molar ratio of the starting materials and reagents to be used in the reaction can be freely determined, but the ratio is preferably such that carbon tetrabromide or tetrachloride, trialkylphosphine or triarylphosphine, and zinc are 2 moles, 2 or 4 moles (2 moles when zinc is used), and 2 moles per mole of the aldehyde compound of the general formula [IX], or it is favorable to effect the reaction at a ratio closer thereto.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic solvent extraction and concentration, and the desired compound of the present invention can be isolated. Further, purification can be carried out by an ordinary technique such as chromatography, distillation or recrystallization.

(Production Process D for the present compounds wherein Y and Z are both oxygen)

wherein R and L are each as defined above.
The reaction is preferably effected in an inert solvent in the presence of a suitable base.
Examples of the solvent which can be used are ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as 1,2-dimethoxyethane, tetrahydro-furan, dioxane and dialkyl (e.g., C1-C4) ethers (e.g., diethyl ether, diisopropyl ether); N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulforane, acetonitrile, nitromethane; halogenated hydrocarbons 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.
Examples of the base which can be used are hydroxides of alkali metals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals, such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate; hydrides of alkali metals or alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alkoxides (e.g., C1-C4) such as sodium methoxide, sodium ethoxide and potassium tert-butoxrde; organic bases such as triethylamine and pyridine. If necessary, catalysts such as ammonium salts (e.g.,



furan and dioxane; and halogenated hydrocarbons such as carbon tetrachloride, dichloro-methane, chlorobenzene and dichlorobenzene.
The reaction temperature is usually set within the range of -20°C to 200°C or the boiling point of a solvent used in the reaction.
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.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic solvent extraction and concentration, and the desired compound of the present invention can be isolated. Further, purification can be carried out by an ordinary technique such as chromatography, distillation or recrystallization.
(Production Process F for the present compounds wherein Y and Z are both
1 9 9
oxygen and R is Q5 (with the proviso that A is A ), Qg (with the proviso that A is A ), Q7, Qg or Q]Q (with the proviso that A is A ) [wherein A is oxygen, sulfur or NR and R is as defined above])



Examples of the solvent which can be used are ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as 1,2-dimethoxyethane, tetrahydro-furan, dioxane and dialkyl (e.g., C]-C4.) ethers (e.g., diethyl ether, diisopropyl ether); N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulforane, acetonitrile, nitromethane; halogenated hydrocarbons 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.
Examples of the base which can.be used are hydroxides of alkali metals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals, such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate; hydrides of alkali metals or alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alkoxides (e.g., CpC^ such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; organic bases such as triethylamine and pyridine. If necessary, catalysts such as ammonium salts (e.g., triethylbenzylammonium chloride) may be added to the reaction system at a ratio of 0.01 to 1 mole per mole of the compound 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 the reaction, preferably -5°C to 100°C or the boiling point of a solvent used in the reaction.
The molar ratio of the starting 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.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic solvent extraction and concentration, and the desired compound of the present invention can be isolated. Further, purification can be carried out by an ordinary technique such as chromatography, distillation or recrystallization.
(Production Process G for the present compounds wherein Y and Z are both oxygen and R is Q5 (with the proviso that A is oxygen), Qg (with the proviso that A is oxygen), Q7, Qg or QJQ (with the proviso that A is oxygen))



Examples of the dehydrating agent which can be used are dicyclohexyl-carbodiimide, and dialkyl (e.g., C1-C4) azodicarboxylates (e.g., diethylazodicarboxylate, diisopropylazodicarboxylate)-trialkyl (e.g., C1-C20) phosphine or triarylphosphine (e.g., triphenylphosphine, trioctylphosphine, tributylphosphine).
Examples of the solvent which can be used are hydrocarbons such as benzene, xylene and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydro-furan and dioxane; and halogenated hydrocarbons such as carbon tetrachloride, dichloro-methane, chlorobenzene and dichlorobenzene.
The reaction temperature is usually set within the range of -20°C to 200°C or the boiling point of a solvent used in the reaction.
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.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic solvent extraction and concentration, and the desired compound of the present invention can be isolated. Further, purification 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 trans-

form) and their mixtures at any ratio.
The following are typical examples of the present compound (wherein R is as shown in Tables 1 to 17), which are not to be construed to limit the scope of the present invention.











































































































































































































The aldehyde compound of the general formula [X], which is an intermediate for use in the production of the present compounds, can be produced, for example, according to the following scheme:

wherein all variables are as defined above.
The compounds of the general formula [IV], [V] or [VI], which are intermediate for use in the production of the present compounds, can be produced, for example, according to the following scheme:















The compounds of the general formula [III] or [X], which are intermediates for use in the production of the present compound, can be produced, for example, according to the following scheme:



The compounds of the general formula [II], [XIII] or [XIV], which are intermediates for use in the production of the present compound, can be produced, for example, according to the following scheme;
SCHEME 8
[X] : ,
dehydrating dehydrating
*1) .u*l)
agent J agent
RJ0]R7 when L1 is fp10] R7 when L iS
R^^H-L1 Sdr°Xyl R^+KbH.' £dr°Xyl
R11 base R11 base
k Jp (e.g., potassium k ; P~1 (e.g., potassium
carbonate) carbonate)
■ • when L1 is L I when L is L
R10]R7 RL/CR14)r [R%' RL/CR14)r
R2IQ-^-K:itOOCH2CH=<:x2 r> ^ J p JC L. J p__x JTC
21 22
depro- e.g., when R depro- "e.g., when R is
tection is c6H5CO, tection acetal of formyl,
KOH-MeOH etc. ' diluted acid
(e.g., p-toluene sulfonic acid-H20-acetone)
* +. MR7 R2 (Ru)r
* reduction xt j \/ ^
[vii] ^ OHC-+€H-OOOCH2CH=CX2
(e.g., NaBHA) Dn J^
halogenation (e.g., SOCl2),
mesylation (e.g., MsCl/Et3N)
or
tosylation (e.g., TsCl/Et3N)
[V] *1) : triphenylphosphine-diethylazodicarboxylate etc.

wherein the general formula [XIV] represents the compound [II] wherein L1 is OH when r is 0, the general formula [XIII] represents the compound [II] wherein L1 is L when r is
2.1
0, R is a protecting group (e.g., benzoyl) for alcohols, Ms is mesyl, Ts is tosyl, and other variables are each as defined above.

7 10
wherein the produced compounds are the compound [XIII] or [XIV] wherein R , R and R*1 are all hydrogen and the compound [II] wherein r is 0, and all the variables are each as defined above.
The compound of the general formula [VII] and the alcohol compound of the general formula [VIII], which are intermediates for use in the production of the present compounds, are commercially available or can be produced, for example, according to the following scheme:


wherein L2 is chlorine or bromine, L3 is mesyloxy or tosyloxy, and X is as defined
above.
The present compounds are satisfactory effective for the control of various
noxious insects, mites and ticks, examples of which are as follows:
Hemiptera:
Delphacidae such as Laodelphax striatellus, Nilaparvata lugens and Sogatella furcifera, Deltocephalidae such as Nephotettix cincticeps and Nephotettix virescens, Aphididae, Pentatomidae, Aleyrodidae , Coccidae , Tingidae, Psyllidae , etc.
Lepidoptera:
Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis, Ostrinia nubilalis, Parapediasia teterrella, Notarcha derogata and Plodia interpunctella, Noctuidae such as Spodoptera litura, Spodoptera exigua, Spodoptera litoralis, Pseudaletia separata, Mamestra brassicae, Agrotis ipsilon, Trichoplusia spp., Heliothisspp., Helicoverpa spp. and Earias spp., Pieridae such as Pieris rapae crucivora, Tortricidae such as Adoxophyes spp., Grapholita molesta and Cydia pomonella, Carposinidae such as Carposina

niponensis, Lyonetiidae such as Lyonetia spp., Lymantriidae such as Lymantria spp. and Euproctis spp., Yponomeutidae such as Plutella xylostella, Gelechiidae such as Pectinophora gossypiella, Arctiidae such as Hyphantria cunea^ Tineidae such asTinea translucens and Tineola bisselliella, etc.
Diptera:
Cu/ex such as Culex pipiens pollens and Cutes tritaeniorhynchus, Aedes such as Aedes albopictus and Aedes aegypti, Anopheles such as Anophelinae sinensis, Chironomidae, Muscidae such as Musca domestica and Muscina stabulans, Calliphoridae, Sarcophagidae, Fannia canicularis, Anthomyiidae such as De//a Platura and De/za antigua, Trypetidae, Drosophilidae, Psychodidae, Tabanidae, Simuliidae, Stomoxyinae, etc.
Coleoptera:
Diabrotica such as Diabrotica virgifera and Diabrotica undecimpunctata, Scarabaeidae such as Anomala cuprea and Anomala rufocuprea, Curculionidae such as Lissorphoptrus oryzophilus, Hypera pastica, and Calosobruchys chinensis, Tenebrio-nidae such as Tenebrio molitor and Tribolium castaneum, Chrysomelidae such as Phyllotreta striolata and Aulacophora femoralis, Anobiidae, Epilachna spp. such as Henosepilachna vigintioctopunctata, Lyctidae, Bostrychidae, Cerambycidae, Paederus fuscipes, etc.
Dictvoptera:
Blattella germanica, Periplaneta fuliginosa, Peroplaneta americana, Peri-planeta brunnea, Blatta orientalis, etc.
Thvsanoptera:
Thrips palmi, Thrips hawaiiensis, etc.
Hymenoptera:
Formicidae, Vespidae, Bethylidae, Tenthredinidae such as Athalia rosae japonensis, etc.
Orthoptera:
Gryllotalpidae, Acrididae, etc.













graphy, which afforded 0.32 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(4-phenylbutyloxy)benzene (73% yield), nD260 1.5716.
Production Example 2: Production of compound (77) by production process E
To a solution of 0.30 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)-phenol, 0.16 g of 3-phenoxy-l-propanol and 0.27 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.21 g of diisopropylazodi-carboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.36 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(3-phenoxypropyloxy)benzene (82% yield), nD25"0 1.5762.
Production Example 3: Production of compound (34) by production process E
To a solution of 0.33 g of 4-(3,3-dichloro-2-propenyloxy)-2,6-dichloro-phenol, 0.23 g of m-phenoxybenzyl alcohol and 0.34 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.26 g of diisopropylazodi-carboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 12 hours, the reaction mixture was concentrated, and then mixed with 20 ml of diethyl ether. The precipitate was filtered, and the filtrate was concentrated. The residue was subjected to silica gel chromatography, which afforded 0.31 g of 3,5-dichloro-4-(3-phenoxybenzyl)-l-(3,3-dichloro-2-propenyloxy)-benzene (57% yield), nD255 1.6066.
Production Example 4: Production of compound (35) by production process E
To a solution of 0.46 g of 4-(3,3-dichloro-2-propenyloxy)-2,6-dichloro-phenol, 0.32 g of p-phenoxybenzyl alcohol and 0.46 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.35 g of diisopropylazodi-

carboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 12 hours, the reaction mixture was concentrated, and then mixed with 20 ml of diethyl ether. The precipitate was filtered, and the filtrate was concentrated. The residue was subjected to silica gel chromatography, which afforded 0.51 g of 3,5-dichloro-4-(4-phenoxybenzyl)-l-(3,3-dichloro-2-propenyloxy)-benzene (68% yield), nD255 1.6084.
Production Example 5: Production of compound (63) by production process E
To a solution of 0.30 g of 4-(3,3-dichloro-2-propenyloxy)-2,6-dichloro-phenol, 0.16 g of 4-chloro-(3-phenetyl alcohol and 0.27 g of tripbenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.21 g of diethyl-azodicarboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.32 g of 4-(4-chloro-P-phenetyloxy)-3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)ben-zene (72% yield), nD24-5 1.5868.
Production Example 6: Production of compound (1) by production process A
To a mixture of 600 mg of 3,5-dichloro-4-(l,l,2,2-tetrafluoroethoxy)phenol, 330 mg of potassium carbonate and 10 ml of N,N-dimethylformamide was added dropwise a solution of 340 mg of 1,1,3-trichloro-l-propene dissolved in 3 ml of N,N-di-methylformamide, while stirring at room temperature. After stirring continued at room temperature for 5 hours, the reaction mixture was poured into ice-water, and extracted twice with 40 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 630 mg of 3,5-dichloro-4-(l,l,2,2-tetrafluoroethoxy)-l-(3,3-dichloro-2-propenyloxy)benzene (82% yield), nD246 1.5067.

Production Example 7: Production of compound (41) by production process A
To a mixture of 1.10 g of 3,5-dichloro-4-(4-fluoro-3-phenoxy)benzyloxy-phenol, 0.44 g of potassium carbonate and 20 ml of N,N-dimethylformamide was added dropwise a solution of 0.89 g of 1,1,3-tribromopropene dissolved in 5 ml of N,N-di-methylformamide, while stirring at room temperature. After stirring at room temperature for 7 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 1.16 g of 3,5-di-chloro-4-(4-fluoro-3-phenoxy)benzyloxy-l-(3,3-dibromo-2-propenyloxy)benzene (69% yield), nD22-5 1.6062.
Production Example 8: Production of compound (3) by production process B
To a solution of 0.54 g of 4-(3,3-dichloro-2-propenyloxy)-3,5-dichloro-phenol, 0.24 g of 3,3-dichloroallyl alcohol and 0.49 g of triphenylphosphine dissolved in 15 ml of tetrahydrofuran was added dropwise a solution of 0.38 g of diisopropylazodi-carboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.52 g of 4-(3,3-dichloro-2-propenyloxy)-3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-benzene (70% yield), m.p. 75.8°C.
Production Example 9: Production of compound (47) by production process C
In a reaction vessel were placed 0.26 g of zinc dust, 1.0 g of triphenylphosphine, 1.3 g of carbon tetrabromide and 20 ml of methylene chloride, followed by stirring at room temperature. After 24 hours, a solution of 0.70 g of (4-(2-chlorobenzyl-oxy)-3,5-dichlorophenoxy)acetaldehyde dissolved in 5 ml of methylene chloride was added dropwise to the above solution, while stirring at room temperature. After stirring at

room temperature for 6 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.63 g of 4-(2-chlorobenzyloxy)-3,5-dichloro-l-(3,3-dibromo-2-propenyloxy)benzene (63% yield), m.p. 83.5°C.
Production .Example 10: Production of compound (23) by production process D
To a mixture of 0.51 g of 2,6-dichloro-4-(3,3,-dichloro-2-propenyloxy)-phenol, 0.27 g of potassium carbonate and 20 ml of N,N-dimethylformamide was added dropwise a solution of 0.29 g of m-chlorobenzyl chloride dissolved in 5 ml of N,N-di-methylformamide, while stirring at room temperature. After stirring at room temperature for 7 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.50 g of 3,5-di-chloro-4-(3-chlorobenzyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene (69% yield), m.p. 87.0°C.
Production Example 11
Production of compound (27) by production process D
To a mixture of 0.72 g of 2,6-dichloro-4-(3,3,-dichloro-2-propenyloxy)-phenol, 0.38 g of potassium carbonate and 20 ml of N,N-dimethylformamide was added dropwise a solution of 0.71 g of 3-fluoro-4-phenoxybenzylbromide dissolved in 5 ml of N,N-dimethylformamide, while stirring at room temperature. After stirring at room temperature for 7 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 1.05 g of 3,5-dichloro-4-(3-fluoro-4-phenoxy)benzyloxy-l-(3,3-dichloro-2-propenyloxy)benzene (86% yield), nD225 1.5973.

Production Example 12: Production of compound (37) by production process E
To a solution of 0.41 g of 4-(3,3-dichloro-2-propenyloxy)-2,6-dichloro-phenol, 0.17 g of a-phenetyl alcohol and 0.37 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.29 g of diisopropylazodi-carboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 12 hours, the reaction mixture was concentrated, and then mixed with 20 ml of diethyl ether. The precipitate was filtered, and the filtrate was concentrated. The residue was subjected to silica gel chromatography, which afforded 0.27 g of 3,5-dichloro-4-oc-phenetyloxy-l-(3,3-dichloro-2-propenyloxy)-benzene (48% yield), nD26'0 1.5830.
Production Example 13: Production of compound (42) by production process E
To a solution of 0.30 g of 4-(3,3-dichloro-2-propenyloxy)-2,6-dichloro-phenol, 0.12 g of (3-phenetyl alcohol and 0.27 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.21 g of diisopropylazodi-carboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 12 hours, the reaction mixture was concentrated and mixed with 20 ml of diethyl ether. The precipitate was filtered, and the filtrate was concentrated. The residue was subjected to silica gel chromatography, which afforded 0.25 g of 3,5-dichloro-4-p-phenetyloxy-l-(3,3-dichloro-2-propenyloxy)benzene (61% yield), nD28-5 1.5816.
Production Example 14: Production of compound (19) by production process D
To a mixture of 0.51 g of 2,6-dichloro-4-(3,3,-dichloro-5-propenyloxy)-phenol, 0.27 g of potassium carbonate and 20 ml of N^-dimethylformamide was added dropwise a solution of 0.31 g of 2-(oc-chloromethyl)naphthalene dissolved in 5 ml of N,N-dimethylformamide, while stirring at room temperature. After stirring at room

temperature for 7 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.58 g of 3,5-dichloro-4-(2-naphthylmethyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene (76% yield), m.p. 86.7°C.
Production Example 15: Production of compound (16) by production process D
To a mixture of 0.62 g of 2,6-dichloro-4-(3,3,-dichloro-2-propenyloxy)-phenol, 0.33 g of potassium carbonate and 20 ml of N,N-dimethylformamide was added dropwise a solution of 0.43 g of cinnamyl bromide dissolved in 5 ml of N,N-dimethyl-formamide, while stirring at room temperature. After stirring at room temperature for 7 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.70 g of 3,5-dichloro-4-(cinnamyloxy)-l-(33-dichloro-2-propenyloxy)benzene (80% yield), m.p. 51.3°C.
Production Example 16: Production of compound (68) by production process D
To a mixture of 0.51 g of 2,6-dichloro-4-(3,3,-dichloro-2-propenyloxy)-phenol, 0.17 g of potassium carbonate and 20 ml of N,N~dimethylformamide was added dropwise a solution of 0.34 g of 2-fluoro-5-(4-fluorophenoxy)benzyl bromide dissolved in 5 ml of N,N-dimethylformamide, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.50 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(2-fluoro-5-(4-fluorophenoxy)

benzyloxy)benzene (68% yield), nD26*0 1.5871.
Production Example 17: Production of compound (84) by production process E
To a solution of 0.30 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)-pfrenol, 0.16 g of 3-chlorophenetyl alcohol and 0.27 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.21 g of diisopropylazodi-carboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.36 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(2-(3-chlorophenyl)ethoxy)-benzene (81% yield), nD260 1.5897.
Production Example 18: Production of compound (86) by production process E
To a solution of 0.30 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)-phenol, 0.20 g of 3-(trifluoromethyl)phenetyl alcohol and 0.27 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.21 g of diiso-propylazodicarboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.39 gof 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(2-(3-(trifluoro-methyl)phenyl)ethoxy)benzene (81% yield), nD260 1.5497.
Production Example 19: Production of compound (91) by production process E
A mixture of 1.14 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)phenol, 1.20 g of 3-(4-chlorophenoxy)propyl bromide, 0.83 g of potassium carbonate and 20 ml of N,N-dimethylformamide was stirred at 80°C for 6 hours. The reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and

concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 1.01 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(3-(4-chlorophenoxy)propyloxy)benzene (55% yield), nD25.0 1.5822.
Production Example 20: Production of compound (99) by production process E
To a solution of 0.30 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)-phenol, 0.24 g of 3-(4-bromophenoxy)-l-propanol and 0,27 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.21 g of diiso-propylazodicarboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.34 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(3-(4-bromo-phenoxy)propyloxy)benzene (65% yield), nD 1.5917.
Production Example 21: Production of compound (100) by production process E
To a solution of 0.30 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)-phenol, 0.25 g of 3-(4-trifluoromethoxy)phenoxy)-l-propanol and 0.27 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise a solution of 0.21 g of diisopropylazodicarboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.41 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(3-(4-(trifluoromethoxy)phenoxy)propyloxy)benzene (78% yield), n25.01.5342.
Production Example 22: Production of compound (166) by production process F
A mixture of 0.56 g of 3,5-dichloro-4-(3-bromopropyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 0.22 g of 4-trifluoromethylphenol, 0.21 g of potassium carbonate and 20 ml of N,N-dimethylformamide was stirred at room temperature. After

stirring for 7 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.48 g of 3,5-di-chloro-4-(3-(4-trifluoromethylphenoxy)propyloxy)-l-(3,3-dichloro-2-propenyloxy)-benzene (71% yield), nD244 1.5390.
Production Example 23: Production of compound (203) by production process F
A mixture of 0.88 g of 3,5-dichloro-4-(4-bromobutyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 0.32 g of 4-isopropoxyphenol, 0.32 g of potassium carbonate and 20 ml of N,N-dimethylformamide was stirred at room temperature. After 7 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.54 g of 3,5-dichloro-4-(4-(4-iso-propoxyphenoxy)butyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene (51% yield), nD 1.5578.
Production Example 24: Production of compound (222) by production process F
A mixture of 0.61 g of 3,5-dichloro-4-(4-bromobutyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 0.19 g of 4-chlorophenol, 0.22 g of potassium carbonate and 20 ml of N,N-dimethylformamide was stirred at room temperature. After 7 hours, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.54 g of 3,5-dichloro-4-(4-(4-chlorophenoxy)buty!oxy)-l-(3,3-dichloro-2-propenyloxy)benzene (59% yield), m.p. 54.5°C.

Production Example 25: Production of compound (152) by production process F
In a reaction vessel were placed 0.29 g of 3,5-dichloro-4-(3-bromopropyl-oxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 0.12 g of 4-ethoxybenzoic acid, 0.12 g of
potassium carbonate and 10 ml of N,N-dimethylformamide, followed by stirring at room temperature for 12 hours. The reaction mixture was poured into water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate> and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.30 g of 3,5-dichloro-4-(3-(4-ethoxybenzoyloxy)propyloxy)-l-(3,3-dichloro-2-propenyloxy)-benzene (86% yield), nD240 1.5715.
Production Example 26: Production of compound (235) by production process F
In a reaction vessel were placed 0.20 g of 3,5-dichloro-4-(3-bromopropyl-oxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 0.10 g of 4-chlorophenylacetic acid, 0.08 g of potassium carbonate and 5 ml of N,N-dimethylformamide, followed by stirring at room temperature for 12 hours. The reaction mixture was poured into water, and extracted twice with. 30 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.22 g of 3,5-dichloro-4-(3-(4-chlorophenylacetyloxy)propyloxy)-l-(3,3-dichloro-2-pro-penyloxy)benzene (90% yield), nD220 1.5698.
Production Example 27: Production of compound (236) by production process F
In a reaction vessel were placed 0.20 g of 3,5-dichloro-4-(3-bromopropyl-oxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 0.11 g of 4-chlorocinnamic acid, 0.08 g of potassium carbonate and 5 ml of N,N-dimethylformamide, followed by stirring at room temperature for 12 hours. The reaction mixture was poured into water, and extracted

twice with 30 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.24 g of 3,5-dichloro-4-(3-(4-chlorocinnamoyloxy)propyloxy)-l-(3,3-dichloro-2-propenyloxy) benzene (96% yield), m.p. 62.2°C.
Production Example 27: Production of compound (237) by production process F
In a reaction vessel were placed 0.20 g of 3,5-dichloro-4-(3-bromopropyl-oxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 0.11 g of 4-chlorophenoxyacetic acid, 0.08 g of potassium carbonate and 5 ml of N,N-dimethylformamide, followed by stirring at room temperature for 12 hours. The reaction mixture was poured into water, and extracted twice with 30 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.23 g of 3,5-dichloro-4-(3-(4-chlorophenoxyacetyloxy)propyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene (91% yield), nD220 1.5709.
Production Example 29: Production of compound (185) by production process G
To a solution of 1.10 g of 3,5-dichloro-4-(3-hydroxypropoxy)-l-(3,3-di-chloro-2-propenyloxy)benzene, 0.56 g of 3-trifluoromethoxyphenol and 0.83 g of triphenylphosphine dissolved in 20 ml of tetrahydrofuran was added dropwise a solution of 0.64 g of diisopropylazodicarboxylate dissolved in 10 ml of tetrahydrofuran, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 1.03 g of 3,5-dichloro-4-(3-(4-trifiuoromethoxyphe-noxy)propoxy)-l-(3,3-dichloro~2-propenyloxy)benzene (64% yield), n^ 1.5343.
Production Example 30: Production of compound (276) by production process F

A mixture of 3.9 g of 4-(trifluoromethyl)aniline and 0.50 g of l-(3-bromo-propyloxy)-2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)benzene was stirred at 90°C to 100°C for 3 hours. After cooling to room temperature, the reaction mixture was subjected to silica gel chromatography, which afforded 0.37 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(3-(4-(trifluoromethyl)phenylamino)propyloxy)benzene (62% yield), nD23"5 1.5617.
Production Example 31: Production of compound (277)
A mixture of 0.37 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(3-(4-(trifluoromethyl)phenylarnino)propyloxy)benzene, 0.1 ml of methyl iodide, 0.12 g of potassium carbonate and 10 ml of N,N-dimethylformamide was stirred at 50°C for 3 hours. After cooling to room temperature, the reaction mixture was poured into ice-water, and extracted twice with 50 ml of ethyl acetate. The combined ethyl acetate layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.26 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(3-(methyl(4-(trifluoromethyl)phenyl)amino)propyloxy)benzene (68% yield), nD 1.5593.
Production Example 3 2: Production of compound (182) according to production process F
A mixture of 0.47 g of 4-chlorothiophenol, 1.33 g of l-(3-bromopropyloxy)-2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)benzene, 0.49 g of potassium carbonate and 20 ml of N,N-dimethylformamide was stirred at room temperature for 24 hours. The reaction mixture was poured into ice-water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 1.24 g of l-(3-(4-chlorophenyl-thio)propyloxy)-2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)benzene (81% yield), nD26-0 1.6035.
Production Example 33: Production of compound (268)

A mixture of 0.50 g of l-(3-(4-chlorophenylthio)propyloxy)-2,6-dich!oro-4-(3,3-dichloro-2-propenyloxy)benzene and 20 ml of methylene chloride was stirred under cooling with ice-water, to which 0.26 gof m-chloroperbenzoic acid was added. After stirring at room temperature for 24 hours, the methylene chloride layer was separated, washed successively with saturated aqueous sodium sulfite solution, saturated aqueous sodium hydrogencarbonate solution and saturated saline solution, dried with magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.38 g of l-(3-(4-chlorophenylsulfinyl)-propyloxy)-2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)benzene (73% yield), nD24'5 1.5962.
Production Example 34: Production of compound (285)
A mixture of 0.50 g of l-(3-(4-chlorophenylthio)propyloxy)-2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)benzene and 20 ml of methylene chloride was stirred under cooling with ice-water, to which 0.52 g of m-chloroperbenzoic acid was added. After stirring at room temperature for 24 hours, the methylene chloride layer was separated, washed successively with saturated aqueous sodium sulfite solution, saturated aqueous sodium hydrogencarbonate solution and saturated saline solution, dried with magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.44 g of l-(3-(4-chlorophenylsulfonyl)-propyloxy)-2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)benzene (82% yield), np 1.5863.
Production Example 35: Production of compound (242) by production process E
In a reaction vessel were placed 0.53 g of 4-(3-fluorophenyl)-3-buten-l-ol and 50 ml of ethyl acetate, and the air in the vessel was exchanged for nitrogen. Then, 0.1 g of 10% palladium carbon was added thereto, and the nitrogen in the vessel was exchanged for hydrogen, followed by vigorous stirring at room temperature for 24 hours. After the hydrogen in the vessel was exchanged for nitrogen, the reaction solution was

filtered through a celite bed, and the filtrate was concentrated. The residue was subjected to silica gel chromatography, which afforded 0.48 g of 4-(3-fluorophenyl)-l-buIanol.
To a solution of 0.18 g of 4-(3-fluorophenyl)-l-butanol, 0.30 g of 2,6-di-chloro-4-(3,3-dichloro-2-propenyloxy)phenol and 0.27 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran, a solution of 0.20 ml of N,N-diisopropylazodi-carboxylate dissolved in 5 ml of tetrahydrofuran was added dropwise, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.38 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-(4-(3-fluorophenyl)butyloxy)benzene (83% yield), nD250 1.5620.
Production Example 36: Production of compound (239) by production process E
A mixture of 4.0 g of (3-hydroxypropyl)triphenylphosphonium bromide and 20 ml of tetrahydrofuran was cooled to 0°C, to which 12.5 ml of 1.6 M n-butyl lithium (as a hexane solution) was slowly added dropwise. The reaction mixture was stirred at 0°C for 30 minutes, to which a mixture of 1.24 g of 3-fluorobenzaldehyde and 10 ml of tetrahydrofuran was slowly added dropwise at the same temperature, followed by further stirring at room temperature for 6 hours.. The reaction mixture was poured into ice-water, acidified by the addition of 10% hydrochloric acid, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with saturated saline solution, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.70 g of 4-(3-fluorophenyl)-3-buten-1 -ol.
To a solution of 0.17 g of 4-(3-fluorophenyl)-3-buten-l-ol, 0.30 g of 2,6-di-chloro-4-(3,3-dichloro-2-propenyloxy)phenol and 0.27 g of triphenylphosphine dissolved in 10 ml of tetrahydrofuran was added dropwise & solution of 0.20 ml of N,N-di-isopropylazodicarboxylate dissolved in 5 ml of tetrahydrofuran, while stirring at room temperature. After the stirring was continued at room temperature for 24 hours, the

reaction mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography, which afforded 0.38 g of 3,5-dichloro-l-(3,3-dichloro-2-propenyl-oxy)-4-(4-(3-fluorophenyl)-3-butenyloxy)benzene (84% yield), nD25'5 1.5857.
Production Example 37: Production of compound (270) by production process E
To a mixture of 20.4 g of 1,3-dibromopropane, 7.1 g of potassium carbonate and 100 ml of N,N-dimethylformamide was added dropwise a solution of 9 g of 4-tri-fluoromethoxyphenol dissolved in 30 ml of N,N-dimethylformamide, while stirring at room temperature. After stirring at room temperature for 24 hours, the reaction mixture was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The residue was subjected to silica gel chromatography, which afforded 9.1 g of l-(3-bromopropyloxy)-4-trifluoromethoxybenzene (60% yield).
To a mixture of 0.6 g of 3,5-diethyl-4-[3-(4-(trifluoromethoxy)phenoxy)-propyloxy]phenol thus obtained, 0.21 g of potassium carbonate and 10 ml of N,N-di-methylformamide was added dropwise a solution of 0.30 g of 1,1,3-trichloro-l-propene dissolved in 5 ml of N,N-dimethylformamide, while stirring at room temperature. After stirring at room temperature for 12 hours, the reaction mixture was poured into ice-water, and extracted twice with 100 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.56 g of 3,5-diethyl-4-[3-(4-trifluoromethoxyphenoxy)propyloxy]-l-(3,3-dichloro-2-propenyloxy)benzene (80% yield), nD25-9 1.5115.
Production Example 38: Production of compound (216) by production process D
First, 0.35 g of l-(3-bromopropyloxy)-4-trifluoromethylbenzene (prepared in the same manner as described above for l-(3-bromopropyloxy)-4-trifluoromethoxy-benzene) and 0.2 g of potassium carbonate were dissolved in 100 ml of N,N-dimethyl-formamide, to which 0.3 g of 2-chloro-6-methyl-4-(3,3-dichloro-2-propenyloxy)phenol













































chloro-2-propenyloxy)benzene riD24'0 1.5485
(300) 3-Chloro-5-methyl-4-(4-(4-isopropoxyphenoxy)butyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene nD24'° 1 -5482
(301) 3-Ethyl-5-methyl-4-(4-(4-trifluoromethoxyphenoxy)butyloxy)-l-(3,3-
dichloro-2-propenyloxy)benzene nD23*0 1.5150
(302) 3-Ethyl-5"inethyl-4-(4'(4-trifluoromethylphenoxy)butyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene nD2 1.5221
(303) 3-Ethyl-5-methyl-4-(3-(4-chlorophenoxy)propyloxy)-l-(3,3-dichloro-
2-propenyloxy)benzene ' nD 1.5562
(304) 3-Ethyl-5-methyM-(4-(4-chlorophenoxy)butyloxy)-l-(3,3-dichloro-
2-propenyloxy)benzene nD2L3 1.5554
(305) 3-Ethyl-5-methyl-4-(3-(4-bromophenoxy)propyloxy)-l-(3,3-dichloro-
2-propenyloxy)benzenenD1 -5670
(306) 3-Ethyl-5-methyl-4-(4-(4-bromophenoxy)butyloxy)-l-(3,3-dichloro-
2-propenyloxy)benzene nD ■ 1.5620
(307) 3-Ethyl-5-methyl-4-(3-(4-isopropoxyphenoxy)propyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene nD 1.5430
(308) 3-Ethyl-5-methyl-4-(4-(4-isopropoxyphenoxy)butyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene nD 1.5429
(309) 3,5-Diethyl-4-(4-(4-txifluoromethoxyphenoxy)butyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene
(310) 3,5-Diethyl-4-(4-(4-trifluoromethylphenoxy)butyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene
(311) 3,5-Diethyl-4-(3-(4-chlorophenoxy)propyloxy)-l-(3,3-dichloro-2-
propenyloxy)benzene
(312) 3,5-Diethyl-4-(4-(4-chlorophenoxy)butyloxy)-l-(3,3-dichloro-2-
propenyloxy)benzene
(313) 3,5-Diethyl-4-(3-(4-bromophenoxy)butyloxy)-l-(3,3-dichloro-2-

propenyloxy)benzene
(314) 3,5-Diethyl-4-(4-(4-bromophenoxy)butyloxy)-l-(3,3-dichloro-2-
propenyloxy)benzene
(315) 3,5-Diethyl-4-(3-(4-i sopropoxyphenoxy)propyloxy)-1 -(3,3-dichloro-
2-propenyloxy)benzene
(316) 3,5-Diethyl-4-(4-(4-isopropoxyphenoxy)butyloxy)-l-(3,3-dichloro-2-
propenyloxy)benzene
(317) 3,5-Diisopropyl-4-(4-(4-trifluoromethoxyphenoxy)butyloxy)-l-(3,3-
dichloro-2-propenyloxy)benzene
(318) 3,5-Diisopropyl-4-(3-(4-trifluoromethylphenoxy)propyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene
(319) 3,5-Diisopropyl-4-(4-(4-trifluoromethylphenoxy)butyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene
(320) 3,5-Diisopropyl-4-(3-(4-chlorophenoxy)propyloxy)-l-(3,3-dichloro-
2-propenyloxy)benzene
(321) 3,5-Diisopropyl-4-(4-(4-chlorophenoxy)butyloxy)-l-(3,3-dichloro-2-
propenyloxy)benzene
(322) 3,5-Diisopropyl-4-(3-(4-bromophenoxy)propyloxy)-l-(3,3-dichloro-
2-propenyloxy)benzene
(323) 3,5-Diisopropyl-4-(4-(4-bromophenoxy)butyloxy)-l-(3,3-dichloro-2-
propenyloxy)benzene
(324) 3,5-Diisopropyl-4-(3-(4-isopropoxyphenoxy)propyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene
(325) 3,5-Diisopropyl-4-(4-(4-isopropoxyphenoxy)butyloxy)-l-(3,3-di-
chloro-2-propenyloxy)benzene
The following are production examples for the intermediate compounds of the general formula [IV], [V] or [VI].
Intermediate Production Example 1: Production of intermediate compound 1)

A reaction vessel was charged with 25.5 g of hydroquinone monobenzyl ether, 17.9 g of benzoyl chloride, 0.50 g of tetrabutylammonium bromide and 100 ml of toluene, to which 78.6 g of 10% potassium hydroxide solution was slowly added dropwise, while stirring under ice cooling. After 24 hours, the reaction mixture was made weakly acidic by the addition of 20% hydrochloric acid, and the deposited crystals were collected by filtration. The crystals thus obtained were successively washed with 10% hydrochloric acid and water, and dried, which afforded 38 g of 4-benzyloxyphenyl benzoate (98% yield).
A reaction vessel was charged with 38 g of 4-benzyloxyphenyl benzoate and 500 ml of ethanol, and the air in the vessel was replaced with nitrogen. Then, 1.0 g of 10% palladium carbort was added thereto, and the nitrogen in the vessel was replaced with hydrogen, followed by vigorous stirring at room temperature for 24 hours. The hydrogen in the vessel was replaced with nitrogen, after which the reaction mixture was filtered though celite, and the filtrate was concentrated, which afforded 24.5 g of 4-hydroxyphenyl benzoate (94% yield).
A reaction vessel was charged with 24.5 g of 4-hydroxyphenyl benzoate and 500 ml of carbon tetrachloride, to which a solution of 24.8 g of t-butyl hypochlorite dissolved in 20 ml of carbon tetrachloride was slowly added dropwise, while stirring under ice cooling. After 24 hours, the reaction mixture was poured into water, followed by phase separation. The organic layer (i.e., carbon tetrachloride layer) was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 29.5 g of 3,5-dichloro-4-hydroxyphenyl benzoate (91% yield).
A reaction vessel was charged with 1.54 g of 3,5-dichloro-4-hydroxyphenyl benzoate, 0.83 g of potassium carbonate, 1.53 g of 4-fluoro-3-phenoxybenzyl bromide, and 10 ml of N,N-dimethylformamide, followed by stirring at room temperature for 5 hours. The reaction mixture was poured into water, and extracted twice with 50 m of diethyl ether. The combined ether layer was washed with water, dried with anhydrous

magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 2.32 g of 3,5-dichloro-4-(4-fluoro-3-phenoxybenzyloxy)phenyl benzoate (88% yield).
A reaction vessel was charged with 1.36 g of 3,5-dichloro-4-(4-fluoro-3-phenoxybenzyloxy)phenyl benzoate and 10 ml of methanol, to which 4.2 g of 10% potassium hydroxide solution was slowly added dropwise under ice cooling. After stirring for 1 hour, the reaction mixture was made weakly acidic by the addition of 10% hydrochloric acid, and extracted twice with 50 ml of diethyl ether under salting out. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 0.97 g of 3,5-dichloro-4-(4-fluoro-3-phenoxybenzyl-oxy)phenol (91% yield), m.p. 144.8°C.
Intermediate Production Example 2: Production of intermediate compound 2)
A mixture of 2.27 g of 4-benzoyloxy-2,6-dichlorophenol, 1.29 g of 2-chloro-benzyl chloride, 1.21 g of potassium carbonate and 50 ml of N,N-dimethylformamide was stirred at 80°C for 6 hours. The reaction mixture was cooled to room temperature, poured in ice water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, and dried with anhydrous magnesium sulfate, followed by removal of the solvent by distillation under reduced pressure. The residue was subjected to silica gel chromatography, which afforded 2.87 g of l-benzoyloxy-4-(2-chlorobenzyl-oxy)-3,5-dichlorobenzene (88% yield).
To a mixture of 2.87 g of l-benzoyloxy-4-(2-chlorobenzyloxy)-3,5-dichloro-benzene and 100 ml of methanol was added dropwise 5.1 g of 10% (w/w) aqueous potassium hydroxide solution, while stirring at room temperature. After stirring at room temperature for 6 hours, the reaction mixture was made weakly acidic by the addition of 10% hydrochloric acid, and the methanol was removed by distillation under reduced pressure. The residue was extracted twice with 100 ml of ethyl acetate. The combined ether layer was washed with water, and dried with anhydrous magnesium sulfate,

followed by removal of the solvent by distillation under reduced pressure. The residue was subjected to silica gel chromatography, which afforded 1.17 g of 4-(2-chlorobenzyl-oxy)-3,5-dichlorophenol (55% yield), m.p. 108.3°C.
Intermediate Production Example 3: Production of intermediate compound 264)
A mixture of 27 g of 2~ethyl-6-methylaniline, 36 ml of concentrated sulfuric acid and 100 ml of water was stirred at a temperature of 0-5°C, to which a solution of 16.1 g of sodium nitrite dissolved in 50 ml of water was added dropwise. Then, 150 g of cold water, 1.5 g of urea and 150 g of ice were added thereto.
This aqueous solution was added dropwise to a mixture of 100 ml of sulfuric acid, 100 ml of water and 150 g of sodium sulfate, while heating to 135°C under stirring. At the same time, the mixture was subjected to steam distillation. After completion of the addition, an aqueous solution obtained by the steam distillation was subjected to salting out with sodium chloride, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 16 g of 2-ethyl-6-methylphenol (59% yield).
Then, 16 g of 2-ethyl-6-methylphenol was dissolved in 200 ml of chloroform, followed by stirring at 0°C, to which 56.6 g of tetrabutylammonium tribromide was added in small portions. After stirring at room temperature for 1 hour, the solvent was removed by distillation under reduced pressure, and the residue was dissolved in 300 ml of diethyl ether. The solution was successively washed with 10% hydrochloric acid and water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 23 g of 4-bromo-2-ethyl-6-methylphenol (92% yield).
To a mixture of 10 g of 4-bromo-2-ethyl-6-methylphenol, 14.0 g of l-(3-bromopropyloxy)-4-trifluoromethoxybenzene and 100 ml of N,N-dimethylformamide was added 7 g of potassium carbonate, while stirring at room temperature. After stirring at room temperature for 12 hours, the reaction mixture was poured into ice water, and

extracted twice with 200 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 18.1 g of 4-bromo-2-ethyl-6-methyl-l-[3-(4-trifluoromethoxyphenoxy)propyloxy]ben-zene (90% yield).
Then, 6.6 g of 4-bromo-2-e±yl-6-methyl-l-[3-(4-trifluoromethoxyphenoxy)-propyloxy]benzene was dissolved in 200 ml of tetrahydrofuran, and the solution was stirred at -70°C, to which 9.6 ml of n-butyl lithium solution (in hexane, 1.58 mol/liter) was added dropwise, followed by further stirring at -70°C for 2 hours. To this reaction mixture was added dropwise a solution of 2.2 g of triethoxy borane dissolved in 60 ml of tetrahydrofuran. Then, the reaction mixture was stirred for 1 hour, while wanning to room temperature, and 13 ml of 10% aqueous hydrochloric acid solution was added in small portions, followed by stirring at room temperature for 20 minutes. The tetrahydrofuran layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated, to which 50 ml of toluene was added, and the mixture was heated at 70°C under stirring, to which 6 ml of 30% aqueous hydrogen peroxide solution was added dropwise. The mixture was heated under reflux for 1 hour, and washed once with water, twice with 10% aqueous ammonium ferrous sulfate solution, and once with water. The toluene layer was dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 3.4 g of 3-ethyl-4-[3-(4-trifluoromethoxyphenoxy)propyloxy]-5-methylphenol (61% yield), nD25-4 1.4955.
Intermediate Production Example 4: Production of intermediate compound 263)
To a mixture of 10 gof 4-bromo-2,6-diethylphenol, 13.5 g of l-(3-bromopro-pyloxy)-4-trifluoromethoxybenzene and 100 ml of N,N-dimethylformamide was added 6.6 g of potassium carbonate, while stirring at room temperature. After stirring at room temperature for 12 hours, the reaction mixture was poured into ice water, and extracted

twice with 200 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 14.8 g of 4-bromo-2-ethyl-6-methyl-1-[3-(4-trifluoromethoxyphenoxy)propyloxy]benzene (76% yield).
Then, 7.0 g of 4-bromo-2-ethyl-6-methyl-l-[3-(4-trifluoromethoxyphenoxy)-propyloxy]benzene was dissolved in 200 ml of tetrahydrofuran, followed by stirring at -70°C, to which 10.0 ml of n-butyl lithium solution (in hexane, 1.58 mol/liter) was added dropwise, followed by further stirring at -70°C for 2 hours. To this reaction mixture was added dropwise a solution of 2.4 g of trimethoxy borane dissolved in 60 ml of tetrahydrofuran. The reaction mixture was stirred for 1 hour, while warming to room temperature, and 13 ml of 10% aqueous hydrochloric acid solution was added in small portions, followed by stirring at room temperature for 20 minutes. The tetrahydrofuran layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated, to which 50 ml of toluene was added, and the mixture was heated at 70°C under stirring, to which 6 ml of 30% aqueous hydrogen peroxide solution wets added dropwise. The mixture was heated under reflux for 1 hours, and washed once with water, and twice with 10% aqueous ammonium ferrous sulfate solution and once with water. The toluene layer was dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 4.3 g of 3,5-diethyl-4-[3-(4-trifluoromethoxyphenoxy)propyloxy]phenol (50% yield), nD 1.5060.
The following are specific examples of the intermediate compounds of the general formula [IV], [V] or [VI] under the corresponding compound numbers with their physical properties, if measured.
1) 3,5-Dichloro-4-(4-fluoro-3-phenoxybenzyloxy)phenol
m.p. 144.8°C
2) 4-(2-ChlorobenzyIoxy)-3,5-dichlorophenol m.p. 1O8.3°C


























Intermediate Production Example 5: Production of 4-(2-chlorobenzyloxy)-3,5-dichlorophenoxyacetaldehyde
A mixture of 0.85 g of 4-(2-chlorobenzyloxy)-3,5-dichlorophenol, 0.47 ml of bromoacetaldehyde diethyl acetal, 0.46 g of potassium carbonate and 20 ml of N,N-di-methylformamide was stirred at 90°C for 6 hours. After cooling to room temperature, the reaction mixture was poured into ice water, and extracted twice with 50 ml of diethyl ether. The combined ether layer was washed with water, and dried with anhydrous

magnesium sulfate, followed by removal of the solvent by distillation under reduced pressure. The residue was subjected to silica gel chromatography, which afforded 0.85 g of 4-(2-chlorobenzyloxy)-3,5-dichlorophenoxyacetaldehyde diethyl acetal (72% yield).
Then, 0.85 g of 4-(2-chlorobenzyloxy)-3,5-dichlorophenoxyacetaldehyde diethyl acetal was dissolved in 10 ml of acetic acid, to which 1 ml of concentrated hydrochloric acid was added dropwise, while stirring under ice cooling. After stirring under ice cooling for 2 hours, the reaction mixture was poured into ice water, and extracted twice with diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, followed by removal of the solvent by distillation under reduced pressure, which afforded 0.70 g of 4-(2-chlorobenzyloxy)-3,5-dichlorophenoxy-acetaldehyde in crude form.
The following are production examples for the intermediate compounds of the general formula [III] or [X].
Intermediate Production Example 6: Production of intermediate compound 317)
A reaction vessel was charged with 30.5 g of 4-hydroxyphenyl benzoate, 21.6 g of potassium carbonate, 20.8 g of 1,1,3-trichloropropene and 100 ml of N,N-di-methylformamide. After stirring at room temperature for 15 hours, the reaction mixture was poured into water, and extracted twice with 150 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 44.1 g of 4-(3,3-dichloro-2-propenyloxy)phenyl benzoate (96% yield).
A reaction vessel was charged with 44.1 g of 4-(3,3-dichloro-2-propenyl-oxy)phenyl benzoate and 400 ml of methanol, to which 33 g of 30% potassium hydroxide was slowly added dropwise under ice cooling. After stirring for 1 hour, the reaction mixture was made weakly acidic by the addition of 10% hydrochloric acid, and extracted twice with 150 ml of diethyl ether under salting out. The combined ether layer was

washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 26.0 g of 4-(3,3-dichloro-2-propenyloxy)phenol (87% yield).
A reaction vessel was charged with 26.0 g of 4-(3,3-dichloro-2-propenyl-oxy)phenol and 500 ml of carbon tetrachloride, to which a solution of 27.1 g of tert-butyl hypochlorite dissolved in 20 ml of carbon tetrachloride was slowly added dropwise, while stirring under ice cooling. After 24 hours, the reaction mixture was poured into water, followed by phase separation. The organic layer (i.e., carbon tetrachloride layer) was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 11.0 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)phenol (32% yield), nD22-5 1.5895.
Intermediate Production Example 7; Production of intermediate compound 325)
A solution of 50 g of 4-bromo-6-chloro-2-methylphenol and 42.5 g of benzyl bromide dissolved in 200 ml of N,N-dimethylformamide was stirred at room temperature, to which 37.4 g of potassium carbonate was added, and the mixture was stirred for 12 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the residue was added to 400 ml of diethyl ether, washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 63 g of 4-bromo-6-chloro-2-methyl- 1-benzyloxybenzene (90% yield).
Then, 40 g of 4-bromo~6-chloro-2-rnethyl- 1-benzyloxybenzene was dissolved in 400 ml of tetrahydrofuran, followed by stirring at -70°C, to which 76 ml of n-butyl lithium solution (in hexane, 1.69 mol/liter) was added dropwise, followed by further stirring at -70°C for 2 hours. To this reaction mixture was added dropwise a solution of 13.3 g of trimethoxyborane dissolved in 50 ml of tetrahydrofuran. Then, the reaction mixture was stirred for 1 hours, while warming to room temperature, and 100 ml

of 10% aqueous hydrochloric acid solution was added in small portions, followed by stirring for 20 minutes. The tetrahydrofuran layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated. The residue was mixed with 200 ml of toluene, and heated at 70°C under stirring, to which 36 ml of 30% aqueous hydrogen peroxide solution was added dropwise. After heating under reflux for 1 hour, the reaction mixture was washed once with water, twice with 10% aqueous ammonium ferrous sulfate solution, and once with water, followed by phase separation. The toluene layer was dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 29 g of 4-benzyloxy-3-chloro-5-methylphenol (91% yield).
To a solution of 27.3 g of 4-benzyloxy-3-chloro-5-methylphenol dissolved in 250 ml of chloroform and stirred at 0°C were added 15.4 g of benzoyl chloride and then 13.3 g of triethylamine. After stirring at room temperature for 2 hours, the chloroform layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel chromatography, which afforded 35 g of 4-benzyloxy-3-chloro-5-methyl-l-benzoyloxybenzene (90% yield).
A reaction vessel was charged with 35 g of 4-benzyloxy-3-chloro-5-methyl-1-benzoyloxybenzene and 200 ml of ethyl acetate, and the air in the vessel was replaced with nitrogen. Then, 2 g of 10% palladium carbon was added, and the nitrogen in the vessel was replaced with hydrogen, followed by vigorous stirring at room temperature for 10 hours. The hydrogen in the vessel was replaced with nitrogen, after which the reaction mixture was filtered, and the filtrate was concentrated. The residue was silica gel chromatography was subjected to silica gel chromatography, which afforded 25 g of 4-benzoyloxy-2-chloro-6-methylphenol (96% yield).
Then, 25 g of 4-benzoyloxy-2-chloro-6-methylphenol was dissolved in 250 ml of chloroform, to which 12 g of chloromethyl methyl ether was added, while stirring at 0°C,.and 21 g of N-ethyldiisopropylamine was added dropwise. After heating under reflux for 1 hour, the chloroform layer was washed with water, and concentrated.

The residue was subjected to silica gel chromatography, which afforded 27.4 g of 3-chloro-4-methoxymethoxy-5-methyl-l-benzoyloxybenzene (96% yield).
Then, 26 g of 3-cMoro-4-methoxymethoxy-5-methyl-l-benzoyloxybenzene was dissolved in 200 ml of methanol, and the solution was stirred at room temperature, while adding dropwise 60 ml of 10% aqueous potassium hydroxide solution. After completion of the reaction, the solvent was removed by distillation under reduced pressure. The residue was added to 150 ml of water, neutralized with 10% aqueous hydrochloric acid solution, and extracted with 200 ml of diethyl ether. The solvent was removed by distillation under reduced pressure, and the residue was subjected to silica gel chromatography, which afforded 17.4 g of 3-chloro-4-methoxymethoxy-5-methylphenol (96% yield).
To a mixture of 10 g of 3-chloro-4-methoxymethoxy-5-methylphenol, 7 g of potassium carbonate and 100 ml of N,N-dimethylformamide was added dropwise a solution of 8 g of 1,1,3-trichloro-l-propene dissolved in 30 ml of N,N-dimethylformamide, while stirring at room temperature. After stirring at room temperature for 12 hours, the reaction mixture was poured into ice water, and extracted with 200 ml of diethyl ether. The combined ether was washed with water, dried with anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel chromatography, which afforded 14.1 g of 3-chloro-4-methoxymethoxy-5-methyl-l-(3,3-dichloro-2-propenyl-oxy)benzene (91% yield).
Then, 14.1 g of 3-chloro-4-methoxymethoxy-5-methyl-l-(3,3-dichloro-2-pro-penyloxy)benzene was dissolved in 100 ml of 80% aqueous acetic acid solution, followed by heating under reflux with stirring for 1 hour. After completion of the reaction, the reaction mixture was mixed with 200 ml of water, and extracted twice with 200 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel chromatography, which afforded 11.3 gof 2-chloro-6-methyl-(3,3-dichloro-2-propenyloxy)phenol (93% yield), m.p. 70.0°C.





A reaction vessel was charged with 10.6 g of 1,3-dibromopropane, 5.53 g of potassium carbonate and 100 ml of N,N-dimethylformamide, to which a solution of 30.5 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)phenol dissolved in 40 ml of N,N-dimethylformamide was slowly added dropwise. After stirring at room temperature for 24 hours, the reaction mixture was poured into water, and extracted twice with 150 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 11.1 g of 3,5-dichloro-4-(3-bromopropyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene (77% yield), nD24'0 1.5693.
Intermediate Production Example 9: Production of intermediate compound 365)
A reaction vessel was charged with 22.67 g of 1,4-dibromobutane, 11.06 g of potassium carbonate and 200 ml of N,N-dimethylformamide, to which a solution of 20.16 g of 2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)phenol dissolved in 80 ml of N,N-dimethylformamide was slowly added dropwise. After stirring at room temperature for 24 hours, the reaction mixture was poured into water, and extracted twice with 300 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 21.7 g of 3,5-dichloro-4-(4-bromobutyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene (74% yield), n^ 1.5666.
The following are production examples for the intermediate compounds of general formula [II] or [XIV].
Intermediate Production Example 10: Production of intermediate compound 367)
A reaction vessel was charged with 11.1 g of 3,5-dichloro-4-(3-bromo-propyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 3.31 g of benzoic acid, 3.90 g of potassium carbonate and 50 ml of N,N-dimethylformamide. After stirring at room temperature for 24 hours, the reaction mixture was poured into water, and extracted twice

with 150 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 11.6 g of 3,5-dichloro-4-(3-benzoyloxypropyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene (95% yield).
A reaction vessel was charged with 11.6 g of 3,5-dichloro-4-(3-benzoyloxy-propyloxy)-l-(3,3-dichloro-2-propenyloxy)benzene, 15.2 g of 10% aqueous potassium hydroxide solution and 300 ml of methanol. After stirring at room temperature for 24 hours, and the reaction mixture was concentrated. The concentrate was poured into water, and extracted twice with 150 ml of diethyl ether. The combined ether layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography, which afforded 7.41 g of 3-(2,6-dichloro-4-(3,3-dichloro-2-propenyloxy)phenoxy)-l-propyl alcohol (83% yield), m.p. 56.6°C.
The following are specific examples of the intermediate compounds of the general formula [II], [XIII] or [XIV] under the corresponding compound numbers with their physical properties, if measured.





















penyloxy)benzene
The following are formulation examples in which "parts" are by weight and the present compounds are designated by the corresponding compound numbers as described above.

Formulation Example 1: Emulsifiable concentrates
Ten parts of each of the present compounds (1) to (325) are dissolved in 35 parts of xylene and 35 parts of N,N-dimethylformamide, to which 14 parts of polyoxy-ethylene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added, and the mixture is well stirred to give a 10% emulsifiable concentrate of each compound.
Formulation Example 2: Wettable powders
Twenty parts of each of the present compounds (1) to (325) are added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine powder and 54 parts of diatomaceous earth, and the mixture is stirred with a mixer to give a 20% wettable powder of each compound.
Formulation Example 3: Granules
To 5 parts of each of the present compounds (1) to (325) are added 5 parts of synthetic hydrated silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay, and the mixture is well stirred. Then, a suitable amount of water is added to the mixture, which is further stirred, granulated with a granulator and then air-dried to give a 5% granule of each compound.
Formulation Example 4: Dusts
One part of each of the present compounds (1) to (325) is dissolved in a suitable amount of acetone, to which 5 parts of synthetic hydrated silicon oxide fine powder, 0.3 part of PAP and 93.7 parts of clay are added, and the mixture is stirred with a mixer. The removal of acetone by evaporation gives a 1% dust of each compound.
Formulation Example 5: Flowables
Twenty parts of each of the present compounds (1) to (325) are mixed with 1.5 parts of sorbitan trioleate and 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and the mixture is pulverized into fine particles having a particle size of not more than 3 (im with a sand grinder, to which 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate are added and then 10 parts of propylene glycol are added. The mixture is stirred to give a

20% water-based suspension of each compound.
Formulation Example 6: Oil solutions
First, 0.1 part of each of the present compounds (1) to (325) is dissolved in 5 parts of xylene and 5 parts of trichloroethane. Then, the solution was mixed with 89.9 parts of deodorized kerosine to give a 0.1% oil solution of each compound.
Formulation Example 7: Oil-based aerosols
First, 0.1 part of each of the present compounds (1) to (325), 0.2 part of tetramethrin, 0.1 part of d-phenothrin, and 10 parts of trichloroethane are dissolved in 59.6 parts of deodorized kerosine, and the solution is put in an aerozol vessel. Then, the vessel is equipped with a valve, through which 30 parts of a propellant (liquefied petroleum gas) are charged under increased pressure to give an oil-based aerosol of each compound.
Formulation Example 8: Water-based aerosols
An aerosol vessel is filled with 50 parts of pure water and a mixture of 0.2 part of each of the present compounds (1) to (325), 0.2 part of d-allethrin, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosine and 1 part of an emulsifier [ATMOS 300 (registered trade name by Atlas Chemical Co.)]. Then, the vessel is equipped with a valve, through which 40 parts of a propellant (liquefied petroleum gas) are charged under pressure to give a water-based aerosol of each compound.
Formulation Example 9: Mosquito-coils
First, 0.3 g of each of the present compounds (1) to (325) is mixed with 0.3 g of d-allethrin, and the mixture is dissolved in 20 ml of acetone. The solution is uniformly mixed with 99.4 g of a carrier for mosquito-coils (prepared by mixing Tabu powder, pyrethrum marc powder and wood flour in the ratio of 4 : 3 : 3) under stirring. The mixture is well kneaded with 120 ml of water, molded and dried to give a mosquito-coil of each compound.
Formulation Example 10: Electric mosquito-mats

First, 0.4 g of each of the present compounds (1) to (325), 0.4 parts of d-aUethrin and 0.4 g of pipenyl butoxide are dissolved in acetone to have a total volume of 10 ml. Then, 0.5 ml of the solution is uniformly absorbed in a substrate for electric mosquito-mats having a size of 2.5 cm x 1.5 cm x 0.3 cm (prepared by forming a fibrillated mixture of cotton linter and pulp into a sheet) to give an electric mosquito-mat of each compound.
Formulation Example 11: Heating smoke formulations
First, 100 mg of each of the present compounds (1) to (325) is-dissolved in a suitable amount of acetone. Then, the solution is absorbed in a porous ceramic plate having a size of 4.0 cm x 4.0 cm x 1.2 cm to give a heating smoke formulation of each compound.
Formulation Example 12: Poison baits
First, 10 mg of each of the present compounds (1) to (325) is dissolved in 0.5 ml of acetone, and the solution is uniformly mixed with 5 g of solid bait powder for animals (Breeding Solid Feed Powder CE-2, trade name by Japan Clea Co., Ltd.). Then, the removal of acetone by air drying gives a 0.5% poison bait of each compound.
The following Test Examples demonstrate that the present compounds are useful as an active ingredient of insecticidal/acaricidal agents. In these Test Examples, the present compounds are designated by the corresponding compound numbers as described above and the compounds used for comparison are designated by the corresponding compound symbols as shown in Table 18.


Test Example 1: Insecticidal test against Spodoptera litura
A 200-fold dilution containing an active ingredient at 500 ppm, which had been prepared by diluting with water an emulsifiable concentrate of the test compound obtained according to Formulation Example 1, was absorbed at a volume of 2 ml in 13 g of an artificial diet for Spodoptera litura, which had been prepared in a polyethylene cup having a diameter of 11 cm. Ten fourth-instar larvae of Spodoptera litura were set free in the cup. After 6 days, the survival of larvae was examined to determine the mortality. The test was conducted in duplicate.
As a result, it was found that the present compounds (l)-(39), (41)-(49), (51)-(66), (68)-(72), (74)-(86)t (88)-(101), (104)-(172), (174)-(189), (191), (193)-(200), (202)-(246), (248), (250)-(274), (276)-(279), (284)-(286) and (288)-(308) exhibited the mortality of 80% or more. In contrast, both compounds (A) and (B) for comparison exhibited the mortality of 0%.
Test Example 2: Test against Tetranychus urticae Koch
Ten female adults of Tetranychus urticae Koch per one leaf were allowed to parasitize to a potting bean at the primary leaf stage harvested for 7 days after seeding, and these pots were placed in a thermostated room at 25°C. After 6 days, a chemical solution containing an active ingredient at 500 ppm, which had been prepared by diluting with water an emulsifiable concentrate of the test compound obtained according to Formulation Example 1, was sprayed at a volume of 15 ml over each pot on a turntable. At the same time, 2 ml of the same solution was drenched in the soil. After 8 days, the degree of damage on the respective plants caused by Tetranychus urticae Koch was examined. The effects were determined according to the following criteria:
-: Damage is scarcely observed.
+: Damage is slightly observed.
-H-: Damage is observed at the same level as in the non-treated field.
As a result, it was found that the present compounds (7)-(8), (25)-(27), (42)-(43), (49), (63), (69)-(72), (76), (77), (102), (104), (119), (120) and (252) were

evaluated as "-" or "+". In the contrast, both compounds A and B for comparison were evaluated as"++".
Test Example 3: Insecticidal test against Heliothis virescens A dilution containing an active ingredient at 100 ppm, which had been prepared by diluting with water an emulsifiable concentrate of the test compound obtained according to Formulation Example 1, was incorporated at a volume of 0.2 ml in an artificial diet. Some second-instar larvae of if. virescens were given the diet and bred in a plastic vessel. After 6-7 days, the mortality was determined.
As a result, it was found that the present compounds (27), (34), (35), (42), (43), (54)-(57), (60), (64), (65), (68)-(70), (77), (81), (84)-(86), (88)-(92), (98)-(101), (107), (108), (112), (114M116), (119), (122), (124), (125), (127)-(129), (139), (142), (146), (147), (164), (166), (185), (202), (203), (222), (224)-(226)s (229), (233), (262), (263) and (272) exhibited the mortality of 80% or more. In contrast, both compounds (A) and (B) for comparison exhibited the mortality of 0%.
Test Example 4: Insecticidal test against Plutella xylostella A chemical solution containing an active ingredient at 50 ppm, which had been prepared by diluting an emulsifiable concentrate of the test compound obtained according to Formulation Example 1 with water containing spreading agent RINOU (Nihon Nouyaku K.K.) to a degree such that the spreading agent had been 1000-fold diluted, was sprayed at a volume 25 ml over each pot of a potting cabbage at the five leaf stage. The treated plants were air dried, on which ten third-instar larvae of Plutella xylostella were set free. After 4 days, the mortality was determined.
As a result, it was found that the present compounds (27), (63)-(65), (68), (70), (77), (81), (84), (98), (100), (101), (106), (108), (111), (120), (130), (139)-(142), (145)-(147), (149H153), (157)-(159), (162), (164)-(166), (185), (188), (199), (202)-(204), (209), (212), (214), 9216), (222)-(234), (236), (242), (246), (250), (251), (259), (260), (262), (263), (267), (272), (284), (292), (294)-(296), (299)-(302), (304), (306) and (308) exhibited the mortality of 80% or more. In contrast, both compounds

(A) and (B) for comparison exhibited the mortality of 0%.
Industrial Applicability
The present compounds have excellent insecticidal/acaricidal activity, so that they are satisfactorily active for the control of noxious insects, mites and ticks.
Our co-pending application no.963/MAS/95 relates to Dihalopropene compounds and insecticidal composition containing the same.

WE CLAIM:
1. A compound of the general formula:

Documents:

1754-06.rtf

1754-che-2006 abstract duplicate.pdf

1754-che-2006 claims duplicate.pdf

1754-CHE-2006 CORRESPONDENCE OTHERS.pdf

1754-CHE-2006 CORRESPONDENCE PO.pdf

1754-che-2006 description (complete) duplicate-1.pdf

1754-che-2006 description (complete) duplicate-2.pdf

1754-che-2006 description (complete) duplicate.pdf

1754-che-2006-abstract.pdf

1754-che-2006-claims.pdf

1754-che-2006-correspondnece-others.pdf

1754-che-2006-description(complete).pdf

1754-che-2006-form 1.pdf

1754-che-2006-form 18.pdf

1754-che-2006-form 26.pdf

1754-che-2006-form 3.pdf

1754-che-2006-form 5.pdf

1754-che-2006abs image.jpg


« Previous Patent
Next Patent »
Patent Number 230394
Indian Patent Application Number 1754/CHE/2006
PG Journal Number 13/2009
Publication Date 27-Mar-2009
Grant Date 26-Feb-2009
Date of Filing 25-Sep-2006
Name of Patentee SUMITOMO CHEMICAL COMPANY LIMITED
Applicant Address 27-1, SHINKAWA 2-CHOME, CHUO-KU, TOKYO 104-8260,
Inventors:
# Inventor's Name Inventor's Address
1 SAKAMOTO NORIYASU 2-10-2-232 SONEHIGASHINO-CHO, TOONAKA-SHI, OSAKA-FU,
2 SUZUKI MASAYA 2-14-7 MEFU, TAKARAZUKA-SHI, HYGO-KEN,
3 TSUSHIMA KAZUNORI 2-1-201 YAYOIGAOKA 6-CHOME, SANDA-SHI, HYGO-KEN,
4 UMEDA KIMITOSHI 6-8 AKURANAKA 4-CHOME, SANDA-SHI, HYOGO-KEN,
PCT International Classification Number C07D213/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 243931/1994 1994-10-07 Japan
2 183461/1994 1994-08-04 Japan
3 089737/1995 1995-04-14 Japan