JPH02178247A - Method for separating 3-phenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ethers - Google Patents

Abstract

PURPOSE:To efficiently separate the subject high-purity compounds in high yield by treating 3-phenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ethers containing impurities which are isomers with an acid. CONSTITUTION:A mixture of 3-phenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ethers containing 3-phenoxybenzyl 2-(4-alkoxyphenyl)-1,1-dimethyl ethers (compounds expressed by formula II) expressed by formula I (R is lower alkyl or H; X1 and X2 are H or F; Y1 and Y2 are H, Cl or Br) as impurities is treated with a Lewis acid, e.g. iron chloride, aluminum chloride, copper oxide, zinc chloride or aluminum bromide, at -10 to +120 deg.C for 0.5-20hr to separate the objective compounds, expressed by formula II and excellent in insecticidal and acaricidal activity with low toxicity to fishes in high purity and yield.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to formula (n) [In formula (II), R is a lower alkyl group or a hydrogen atom, and the island and X2 are each a hydrogen atom or a fluorine atom. Yl and Y8 are hydrogen atoms, chlorine atoms or bromine atoms. ], 3-phenoxybenzyl 2
The present invention relates to a method for separating -(4-alkoxyphenyl)-2-methylpropyl ether (hereinafter abbreviated as benzylmethylpropyl ethers).

More specifically, in formula (1) [2N), R, L, X2, Yl and Y8 are represented by the formula (
It has the same meaning as R, XI, Xt, Yl and Yt in II). ] 3-phenoxybenzyl 2-(
4-Alkoxyphenyl)-1,1-dimethylethyl ethers (hereinafter abbreviated as benzyldimethylethyl ethers) as an impurity, the benzylmethylpropyl ethers of the above formula (n) can be efficiently converted to the above formula. A method for separating the compound (II) is provided.

The benzyl methyl propyl ether derivative represented by the formula (II) is known to be a compound having excellent insecticidal and acaricidal activity and low toxicity to fish.

However, regarding pesticides, not only the active ingredients but also
Environmental pollution caused by contained impurities is also a problem, and the presence of impurities caused by raw materials and reactions cannot be ignored, and it is desired to reduce them as much as possible.

[Prior art and problems to be solved by the invention] Conventionally, formula (n) [in formula (n), R, Ls)h, Yl and Y! has the same meaning as the above formula (If). For example, the method for producing benzyl methyl pro- and ethers represented by
-Chloro-4-ethoxy neofiltrarolide and 3-phenoxybenzyl alcohol are reacted in an aprotic polar solvent in the presence of a base to produce the desired condensation compound 3-phenoxybenzyl 2-(3-chloro-4ethoxyphenyl). enyl)-2-methylpropyl ether is obtained. Also, during this reaction, the isomer 3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-1
, 1-dimethylethyl ether are also produced as impurities in non-negligible amounts.

This publication also describes the isomers of dimethyl ethyl benzyl ether of the formula (1) and the benzyl methyl propyl ether of the formula (I[) as unreacted 3-
After removing low-boiling components such as phenoxybenzyl alcohol by distillation, high-boiling components containing the target product are further crystallized to separate the target compound benzyl methyl propyl ethers, or the reaction crude The product is purified by column chromatography to obtain a purified product of benzyl methyl propyl ethers.

However, as is clear from their structures, the target compound benzyl methyl propyl ether represented by the above formula (n) and the isomer benzyl dimethyl ethyl ether represented by the above formula (1) are physically The benzyl methyl propyl ethers represented by the above formula (If) can be easily purified by ordinary purification operations such as distillation, recrystallization, crystallization, or column chromatography, as they have extremely similar physical and chemical properties. is difficult to separate.

The present invention provides the target compound, benzyl methyl propyl ether, from the benzyl methyl propyl ether represented by the formula (f[), which contains benzyl dimethyl ethyl ether as an impurity, represented by the formula (1). The purpose is to separate efficiently.

[Means to solve the problem]

The present inventors pretreated a mixture of the target compound, benzyl methyl propyl ether represented by the above formula (II), and its isomer, the benzyl dimethyl ethyl ether represented by the above formula (1). By carrying out this step, the isomer benzyl dimethyl ethyl ether represented by the above formula (r) is selectively converted into a compound that is easily separated, and the benzyl methyl propyl ether represented by the above formula (II) is efficiently converted. We carefully considered the method of separation.

As a result, by treating the mixture with a Lewis acid such as iron chloride or aluminum chloride, benzyl dimethyl ethyl ethers represented by the above formula (1) are selectively cleaved into ethers, and ether cleavage occurs. It has been found that the compound of the formula (I), which is expressed by the reaction formula (I[[), changes to a compound with a relatively low boiling point as represented by the reaction formula (I [[)].

(The following is a blank space) Reaction formula (III) Furthermore, it has been found that the hensyl methyl propyl ethers represented by the above formula (II) exist stably under predetermined reaction conditions. The present invention has been made based on these findings.

That is, the present invention provides formula (1) [In formula (1), R is a lower alkyl group or a hydrogen atom, xI and Xs are each a hydrogen atom or a fluorine atom, and Y8 and Y2 are a hydrogen atom, a chlorine atom, atom, or a bromine atom. [In formula (II), R, Xls Xs, Yl and Y8 are formulas (1) (7) R, X, , x2, Y+ and Y! Same as. ] The method for separating benzyl methyl propyl ethers of formula (II) from benzyl methyl propyl ethers is characterized by pretreatment with a Lewis acid.

In the method of the present invention, a Lewis acid is added to a mixture of the benzyl dimethyl ether of the formula (1) and the benzyl methyl propyl ether of the formula (n), and the mixture is reacted with the benzyl dimethyl ether represented by the formula (1). To selectively decompose benzyl dimethyl ethers into components having completely different chemical and physical properties, and to advantageously separate benzyl methyl propyl ethers. Moreover, by using predetermined reaction conditions during the reaction, decomposition of the benzyl methyl propyl ether represented by the formula (U) can be suppressed, and the benzyl methyl propyl ether can be obtained in high yield and purity.

The general formula embodiments of the present invention are as follows.

The benzyl dimethyl ethyl ethers represented by the above formula (1) and the benzyl methyl propyl ethers represented by the above formula (n), which are the raw materials used in the method of the present invention, are
According to the method described in Publication No. 10493, β,β-dimethylphenethyl chloride or α,α-dimethylphenethyl chloride and 3-phenoxybenzyl alcohol are easily reacted in an aprotic polar solvent in the presence of a base. It can be synthesized into

At this time, there is no particular restriction on the allowable amount of benzyl dimethyl ethyl ether represented by the above formula (1) mixed in as an impurity, and no matter what proportion it is mixed in, it will not cause problems in the method of the present invention. do not have.

The Lewis acids used in the present invention are all anhydrides, AlCl, AIBr=, FeCl3, FeB
r2.5nC1a, 5nare, CoCIx
, BFs , ZnCIz , ZnBrx , C
Examples include uCIz, CuBr1, etc., but are not limited to these Lewis acids.

In addition, the above Lewis acids are usually used alone, but 2
There is no problem even if more than one type of Lewis acid is used in combination.

Regarding the amount of Lewis acid used, if it is used in excess, it may cause decomposition and side reactions of the target compound, benzyl methyl propyl ethers represented by the above formula (n), so that impurities 0.1 to 1.5 mole times, preferably 0.3 to 1 mole based on the benzyl dimethyl ethyl ether represented by the formula (I) contained as
．． It is 0 mole times. Furthermore, if the lower limit of the amount used is less than 0.1 mol, the reaction rate will be extremely slow or the reaction itself will stop at a certain reaction rate, making it difficult to call it a practical method.

In the present invention, the temperature conditions and reaction time of acid treatment are -
10"C to 120°C for 0.5 to 20 hours, but preferably o'c to 100°C for 14 to 12 hours. If the reaction temperature is lower than 110°C, the reaction rate is extremely slow. Or, the reaction itself does not proceed, or conversely, if the reaction temperature is higher than 120°C, decomposition of the benzyl methyl propyl ether represented by the above formula (II) is likely to occur, and furthermore, side reactions may occur. This is not preferable because it causes a decrease in yield.

Further, when performing the acid treatment, a reaction solvent may be used.

When carrying out the reaction, a Lewis acid is charged in advance into the reactor, and the benzyl methyl propyl ethers of the formula (It), including the benzyl dimethyl ethyl ethers of the formula (1), are separated. Although it is preferable to adjust the reaction temperature to a predetermined temperature after the charging is completed, the order in which the raw materials to be subjected to the reaction are charged is not limited.

In the present invention, when acid treatment is performed, the benzyl dimethyl ethyl ether represented by the formula (1) generates an ether cleavage product as shown in the reaction formula (IV). ) The aluminum bromide alcoholade in reaction (IV) is
Addition of water gives 3-phenoxybenzyl alcohol.

After the acid treatment, the benzyl methyl propyl ethers of formula (II) can be separated by washing the acid treatment solution with water until it becomes neutral, or by adding an aqueous alkali solution etc. to neutralize it, and then washing it with water. The target compound, the benzyl of formula (II), is obtained by neutralizing it, removing the Lewis acid used in the reaction, and subjecting it to separation operations such as distillation, recrystallization, crystallization, or column chromatography. Methyl propyl ethers are obtained.

The present invention thus provides 3-phenoxybenzyl 2-
(3-chloro-4-methoxyphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3゜5
-dichloro-4-methoxyphenyl)-2, methylpropyl ether, 3-phenoxybenzyl 2-(3-bromo 4-methoxyphenyl)-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2- (
3-chloro-4-methoxyphenyl)-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(3,5-dichloro-4-methoxyphenyl)-2
-Methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(3-bromo-4-methoxyphenynoly2-methylpropyl ether, 3-(4-fluorophenoxy)benzyl 2-(3-chloro-4-methoxy) phenyl)-2-methylpropyl ether, 3-(4-
fluorophenoxy)benzyl 2-(3,5-dichloro-4-methoxyphenyl)-2-methylpropyl ether, 3-(4-fluorophenoxy)benzyl 2-(3
-bromo-4-methoxyphenyl)-2-methylbrobyl ether, 3-(4-fluorophenoxy)-4-fluorobenzyl-2-(3-chloro-4-methoxyphenyl)-2-methylpropyl ether, 3 -(4-fluorophenoxy)4-fluorobenzyl 2-(3,5-
dichloro-4-methoxyphenyl)-2-methylpropyl ether, 3-(4-fluorophenoxy)-4-fluorobenzyl 2-(3-bromo-4-methoxyphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-
2-Methylpropyl ether, 3-phenoxybenzyl 2- (3,5-dichloro-4-ethoxyphenyl)-
2-methylpropyl ether, 3phenoxybenzyl 2
-(3-bromo-4-ethoxyphenyl)-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(3-chloro-4-ethoxyphenyl)2-methylpropyl ether, 3-phenoxy-4- Fluorobenzyl 2-(3,5-dichloro-4=ethoxyphenyl)-2-methylpropyl ether, 3-(4-fluorophenoxy)benzyl 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl ether, 3-(4
-fluorophenoxy)benzyl 2(3,5-dichloro-4-ethoxyphenyl)-2-methylpropyl ether, 3-(4-fluorophenoquine)benzyl 2-(3
-bromo-4-ethoxyphenyl)-2=methylpropyl ether, 3-(4-fluorophenoxy)-4-fluorobenzyl 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl ether, 3-( 4-fluorophenoxy)-4-fluorobenzyl 2- (3,5
-dichloro-4-ethoxyphenyl)-2-methylpropyl ether, 3-(4-fluorophenoxy)-4-
Fluorobenzyl 2-(3-bromo-4-ethoxyphenyl)-2-methylpropyl ether, 3-phenoxy-6-fluorobenzyl 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl ether, 3- Phenoxy-6-fluorobenzyl 2-(3,5-dichloro-4-ethoxyphenyl)-2-methylpropyl ether, 3phenoxy-6-fluorobenzyl 2-(3-bromo-4-ethoxyphenyl)-2-methyl Propyl ether, 3-(2-fluorophenoxy)benzyl 2-
(3-chloro-4-ethoxyphenyl)-2-methylpropyl ether, 3-(2-fluorophenoxy)benzyl 2(3,5-dichloro-4-ethoxyphenyl)-
2-Methylpropyl ether, 3-(2-fluorophenoxy)benzyl 2-(3-bromo-4-ethoxyphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-[3-chloro-4-(i- propoxy) phenyl-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,5-dichloro-4-(i-propoxy)phenyl-2-methylpropyl ether, 3
-phenoxybenzyl 2-[3-bromo-4-(i-propoxy)phenyl-2-methylpropyl ether,
3-phenoxy-4-fluorobenzyl 2-(3-chloro-4-(I-propoxy)phenyl-2-methylpro-ether, 3-phenoxy-4-fluorobenzyl 2-(3,5-dichloro-4-(i) -propoxy)phenyl-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(3-bromo 4-(i
-propoxy)phenyl]-2-methylbrobyl ether, 3-phenoxybenzyl 2-[3-chloro-4-(
l-methylpropoxy) phenyl-2-methylpropyl ether, 3-phenoxybenzyl 2- (3,5-
Dichloro-4(1-methylpropoxy)phenyl2
-Methylpropyl ether, 3phenoxybenzyl 2-
(3-bromo 4-(1-methylpropoxy)phenyl-2-methylpropyl ether, 3-phenoxybenzyl 2-[3-chloro-4-(n-butoxy)phenyl-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,5-dichloro-4-(n-butoxy)phenyl-2-methylpropyl ether, 3-phenoxybenzyl 2-(3-bromo-4-(n-butoxy)phenyl-2-methylpropyl ether, 3 -phenoxybenzyl 2-[3-chloro-4-(t-butoxy)phenyl-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,5-dichloro-4-(t-
butoxy) phenyl-2-methylpro and ether,
3-phenoxybenzyl 2-(3-bromo-4-(t-
butoxy) phenyl-2-methylpropyl ether,
3-phenoxybenzyl 2- (3-chloro-4-(n
-pentyloxy)phenyl2-methylpropyl ether, -phenoxybenzyl 2- (3,5-dichloro-4-(n-pentyloxy)phenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-[3
-bromo-4-(n-pentyloxy)phenyl2
-Methylpropyl ether, 3-phenoxybenzyl 2
-(4-Ethoxyphenyl)-2-methylpropyl ether, 3-phenoxybenzyl-4-fluorobenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-methoxyphenyl) -2-Methylpropyl ether, 3-phenoxybenzyl 2-(3-chloro-4-hydroxyphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,5-dichloro-4-hydroxyphenyl)-2 -propyl ether, 3-phenoxybenzyl 2
-(4-hydroxyphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3-bromo-4
-hydroxyphenyl)-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(3-chloro-4-hydroxyphenyl)-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(
It can be applied to a method for separating 3-bromo-4-hydroquinphenyl)-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(4-hydroxyphenyl)-2-methylpropyl ether, and the like.

[Examples] Next, the present invention will be explained in more detail by showing Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-2-methyl protoether 50%, 3
-Phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-1,1-dimethyl ethyl ether (410.9 g) containing 50% of the mixture was charged into a 500-sized 4-tube flask, and chlorinated steel 33.9 g was placed in the flask. Add 6 g (0.5 molar amount relative to benzyl dimethyl ethyl ether Cu) and stir at 100°C for 10 hours. After cooling, drain into water in Step 11 and wash with water, then add 500 d of water. After washing with water three times, the lower organic layer was dehydrated under reduced pressure to obtain 410.1 g of an oily substance.The results of gas chromatography analysis using an internal standard method are as follows.

・3-phenoxybenzyl 2-(3-chloro o-4-ethoxyphenyl)-2-methylpropyl ether
49.8χ (recovery rate 99.4χ)・3-
phenoxybenzyl alcohol
21.3χ・1.1-dimethyl-2-(3-riU3-4-ethoxyphenyl)ethylchloride F27.
0χ ・3-phenoquinbenzyl 2-(3-croto4-ethoxyphenyl)-1,1-dimethylethyl ether
300 g of the oil obtained above was placed in a distillation flask and distilled under reduced pressure in an Nt atmosphere.

The vacuum distillation conditions were as follows: Start heating from room temperature under a reduced pressure of lnmHg, raise the temperature until the distillation pot temperature reaches 160 ° C, 1.
At OmmHg and 160"C, it became impossible to remove 7p of low boiling point components, so the distillation was terminated. Distillation section 143.
7 g and 154.1 g of pot residue were obtained.

The results of gas chromatography analysis of the remaining portion of the pot using the internal standard method were as follows.

・3-7 enoxypencyl 2-(3-riU-4-ethoxyphenyl)-2-methylpropyl ether

96,9χ・3-phenoquine benzyl alcohol
0.5χ・1.1
-dimethyl-2-(3-ri-4-ethoxyphenyl)I-thyl chloride O83z ・3-7 enoxybenzyl 2-(3-chloro-4-ethoxyphenyl butyl ether)-1,1-dimethylethyl ether 1.
8χ Example-2 3-phenoxybenzyl 2-(3-chloro-4
-ethoxyphenyl)-2-methylpropyl ether 7
5%, 3-phenoxybenzyl 2-(4-ethoxyphenyl)-1,1-dimethylethyl ether 25%, 41
0.9g Also FeCl540.6g as Lewis acid (
411.2 g of an oily substance was obtained by carrying out the same operation as in Example 1, except that 5 molar amount of benzyl dimethyl ethyl ether (Fe) was used.Results of gas chromatography analysis using internal standard method is as below.

・3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl ether
73.0χ (survival rate 97.4χ)
・3-phenoxybenzyl alcohol
11.5χ・1,1-dimethyl-2
-(3-Rho-4-ethoxyphenyl)ethylchloride F14.3χ ・3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-11 dimethyl ethyl ether
0.2χ 100g of the oil obtained in this way was
500 g of methaconol was charged into the cylindrical sepulpuru flask, and after stirring vigorously for 5 hours at -10"C, the crystals that had crystallized were filtered using a picofner, and further The crystals remaining as a residue on the filtration were washed with 50 g of methanol that had been cooled in advance to 0° C. The crystals remaining as a residue on the filtration were demethanoled under reduced pressure to obtain 43.2 g of a dry product.

The gas chromatography analysis values using the internal standard method are as follows.

・3-phenoxybenzyl 2-(3-riOI!-44
) xyphenyl)-2-methylpropyl ether

99.3'1-3-phenoxybenzyl alcohol 0.2z-1.
1-ㅅmethyl-2-(3-ri-4-ethoxyphenyl)ethylc [! IJF0.1χ Example-3 13.6 g of zinc chloride (using the same mole as benzyl dimethyl ethyl ether Zn) was charged into a 500 d 4 flask, and 3-phenoxybenzyl 2-(
376.5 g of a mixed solution containing 90% of 4-ethoxyphenyl) to 2-methylpropyl ether, 10% of 3-phenoxybenzyl 2-(4-ethoxyphenyl)-i, and 1-dimethylethyl ether was added, and the mixture was heated at 70°. The mixture was stirred at C for 1 hour, cooled to room temperature, and then discharged into water from Step 12 to complete the reaction. After separating the lower ta layer, further 500
After washing with tel water three times and separating the layers, the lower a layer was separated and dehydrated under reduced pressure to obtain 376.3 g of an oily substance.

The gas chromatography analysis values using the internal standard method are as follows.

・3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether 88.9χ (recovery rate 98.7χ) ・3-phenoxybenzyl 2-(4-ethoxyphenyl)-Ll-methylethyl ether 0.1χ ・3-phenoxybenzyl algol
5.1χ・11-dimethyl-2
-(4-ethoxyphenyl)ethyl chloride 5.
6χ Example-4 3-phenoxybenzyl 2-(4-hydroxyphenyl)-2-methyl pro-ether 80%, 3-phenoxybenzyl 2-(4-hydroxyphenyl)-1,1-
Mixture containing 20% dimethyl ethyl ether 348.4
g was charged into a 500 d four-tube flask, followed by 53.3 g of aluminum bromide (equal molar wall as benzyl dimethyl ethyl ether At" li), and the temperature was raised to 45 °C without stirring. After stirring at 45°C for 3 hours, the mixture was poured into water in Step 11 to complete the reaction.

The lower organic layer was separated and further washed three times with 500-g water. The obtained organic layer was dehydrated under reduced pressure to obtain 350.3 g of an oily substance. The results of gas chromatography analysis using the internal standard method are as follows.

・ 3-phenoxybenzyl 2-(4-HF17XIF-X-Nyl)-2-methylethyl ether 77.7χ (recovery rate 97.7χ) ・ 3-Phenoxybenzyl 2-(4-7FOXIF:5)-1 ,1-dimethylethyl ether
trace·
3-phenoxybenzyl alcohol
10.1χ・1.1-dimethyl-2
-(4-Ethoxyphenyl)ethylbumid F 12
．． 1χ Comparative Example-1 3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl ether 50%, 3
-Fethoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-1,1-dimethylethyl ether (300 g) was charged into a distillation flask and distilled under reduced pressure in an Hz atmosphere. The vacuum distillation conditions were 0. Start raising the temperature from room temperature under a reduced pressure of lmmHg, and bring the distillation pot to a temperature of 230°C.
It ended when it became.

Distillate fraction: 130.0g Residue from pot: 168.3g The gas chromatography analysis values of the distillate portion and the residue from the pot using the internal standard method are as follows.

Distillate fraction: 3-7 enoxypencil 2-(3-riD-4-ethquinfeco1)-2-methylpropyl ether

65,3χ・3-phenoxybenzyl 2-(3-
chloro-4-ethoxyphenyl) to l,1-li thyl ethyl ether
34.5! Bottle residue: 3-phenoxybenzyl 2-(3-chloro-4-ethquinphenyl)-2-methylpropyl ether

37.8X・3-phenoxybenzyl 2-(3-
Chloro 3-4-ethoxyphenyl)-1 1-cymelene ethyl ether
62.0χ Comparative Example-2 3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl ether 50%, 3
- 100g of a mixed solution containing 50% of phetoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-1,1-dimethylethyl ether was charged into a 11-cylindrical separable flask equipped with a baffle, and this After 500 g of methanol was charged into the solution and stirred vigorously for 5 hours at -1 O'C, the crystals that had precipitated were separated by filtration, and the crystals were washed with 50 g of methanol that had been previously cooled to O'C. The crystalline portion was removed from methanol under reduced pressure to obtain 87.8 g of a dry product.The gas chromatography analysis values using the internal standard method are as follows.

・3-7Itsukidibenzyl 2-(3-chloro-4-ethquinphenyl)-2-methylpropylnefur

56.2χ・3-phenoxybenne82-(3-chloro3-4-ethoxypheny3)-1,1-dimethylethyl ether
43.7X [Effect of the Invention] By carrying out the present invention, 3-phenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ethers can be obtained efficiently and with high purity.

Patent Applicant: Mitsui Toatsu Chemical Co., Ltd. (Procedure Wandering 1) (Voluntary) October 1, 1999 Director General of the Japan Patent Office Yoshi 1) Moon Takeshi l, Indication of Case 1988 Patent Application No. 328894 26 Invention Name of 3-Method for separation of phenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ethers 3, Relationship with the case of the person making the amendment Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (31
2) Mitsui Toatsu Chemical Co., Ltd. 4. Number of claims increased by amendment 0 5. Subject of amendment (1) Corrected "dimethyl el dimethyl ethyl ether" on page 5, lines 13 to 14 of the specification. .

I am corrected.

Correct "neck" to "thyl ethyl ethers".

(3) "Benzyl dimethyl ethers" in the fifth line from the bottom of page 9 of the specification is corrected to "benzyl methyl ethyl ethers."

(4) In line 121 of the specification, "Tyle ethyl ethers" is corrected to "Tyle ethyl ethers J."

(5) Lines 11 to 9 from the bottom of No. 13 of the specification [During reaction (rV)... 3-phenoxybenzyl alcohol is given. "The aluminum bromide alcoholade in reaction formula (IV) can be prepared by adding water."
Provides 3-phenoxybenzyl alcohols. ” he corrected.

(6) “1,1-dimethyl-
2(3-chloro-4-ethoxyphenyl)ethyl chloride" is replaced by "I,■-dimethyl-2-(3-chloro-4-ethoxyphenyl)ethyl chloride Jzyl 2-
(3-chloro-4-ethoxyphenyl)-2-methylpropy” is replaced by “3-phenoxybenzyl 2-(3-
Chloro-4-ethoxyphenyl-2-methylpropyl”
I am corrected.

(8) "1,1-dimethyl-2(3-7,col-4-ethoxyphenyl)-ethyl chloride" on page 21, line 18 of the specification is replaced with "1,1-dimethyl-2-ethyl chloride". (3-
chloro-4-ethoxyphenyl)-ethyl chloride”.

(9) "3-phenoxybenzyl 2- (3-chloro- 4-ethoxyphenyl)”.

00) "3-phenoxybenzyl 2-(4-ethoxyphene)" on page 22, line 5 of the specification is corrected to "3-phenoxybenzyl 2-(3-chloro-4-ethoxyphene").

"1,1-dimethyl-" on page 22, line 15 of the θO specification
2-(3-chloro-4-ethoxyphenyl)ethyl chloride J is corrected to ``1,1-dimethyl-2-(3-chloro-4-ethoxyphenyl)ethyl chloride J.

0ri Specification, page 23, line 1: “Reni Methaqunol 50
0g of methanol and 500g of methanol.
I am corrected as follows.

In the second line of page 23 of the specification, the phrase ``The crystallized crystal is Pico'' is corrected to ``The crystallized crystal is Bini J.''

(b) In the 6th line of page 23 of the specification, "43.2 g of dry product was obtained.J" is corrected to "63.2 g of dry product was obtained."

05) On page 24, line 10 of the specification, [3-phenoxybenzyl 2-(4-ethoxyphenyl)-1,1-methyl ethyl ether] has been replaced with "3-phenoxybenzyl 2-(4-ethoxyphenyl)". )-1,1-dimethylethyl ether”.

0ω Specification page 26, line 8, line 10, line 13, line 15, "(3-chloro-4-ethoxyphenyl)" is replaced with "(3-chloro-4-ethoxyphenyl)" correct.

0'I) "(3-
chloro-4-ethoxyphenyl)” is replaced with “(3-chloro-4-ethoxyphenyl)”
chloro-4-ethoxyphenyl)”.

Claims (1)

[Claims] 1. Formula (I) ▲ Includes mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In formula (I), R is a lower alkyl group or a hydrogen atom, and X_1 and X_2 are each a hydrogen atom , or a fluorine atom, and Y_1 and Y_2 are a hydrogen atom, a chlorine atom, or a bromine atom. ] 3-phenoxybenzyl 2-(4-alkoxyphenyl)-1,1-dimethylethyl ethers and formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [Formula (II) In the formula, R is a lower alkyl group or a hydrogen atom, X_1 and X_2 are each a hydrogen atom or a fluorine atom, and Y_1 and Y_2 are a hydrogen atom, a chlorine atom, or a bromine atom. ] Separation of 3-phenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ether from a mixture containing 3-phenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ether represented by 3, characterized in that the mixture is treated with an acid when
-phenoxybenzyl 2-(4-alkoxyphenyl)
-A method for separating 2-methylpropyl ethers. 2. The method according to claim 1, wherein the acid is a Lewis acid. 3. The method according to claim 1, wherein the acid treatment temperature is -10°C or higher and 120°C or lower.