JP3490952B2 - Method for producing diaryloxymethylbenzene compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a diaryloxymethylbenzene compound useful as a sensitizer for a heat-sensitive recording material.

[0002]

2. Description of the Related Art As a method for producing an ether compound using a substituted or unsubstituted phenol compound, a method of reacting a phenol compound with a halogen compound in the presence of an alkali is known. JP-A-3-69391 discloses a method of obtaining a diether compound by reacting a hydroquinone compound with benzyl chloride in a dimethyl sulfoxide solvent in the presence of potassium hydroxide. As a method for producing a diaryloxyalkane, JP-A-61-222239 discloses that a diether compound is obtained by reacting a substituted or unsubstituted phenol compound with a dihalogenated alkane in a dimethylsulfoxide solvent in the presence of potassium carbonate. A method of obtaining is disclosed.
However, since dimethylsulfoxide, which is difficult to recover and expensive by these methods, is used as a solvent, it is difficult to efficiently manufacture the target compound at a low cost.

On the other hand, in JP-A-61-176544 and JP-A-61-260036, an ether is prepared by reacting a sulfonic acid ester of aryloxy alcohol or a sulfonic acid ester of alkylene diol with phenol or aromatic alcohol. Although methods of obtaining the compounds have been disclosed, these methods require the sulfonic acid ester of an aryloxy alcohol or alkylene diol to be once prepared. Further, as a method for producing diaralkyloxymethylbenzene, JP-A-3-71885 is known.
The publication discloses a method for producing an xylenediglycol potassium salt from xylenediglycol and potassium hydroxide in a dimethylsulfoxide solvent, and reacting this with benzyl chloride to obtain an ether compound. Uses dimethylsulfoxide as a solvent, which is expensive and difficult to recover. In addition, this method requires an extraction step such as ether extraction, and thus has a problem that the number of manufacturing steps increases.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and provides a method for efficiently and inexpensively producing a diaryloxymethylbenzene compound in a simple process. With the goal.

[0005]

Means for Solving the Problems The present inventors have found, after intensive studies to achieve the above object, under certain conditions, by reacting a phenol compound and xylene dihalide, anti
After completion of the reaction, alkali metal separated from the reaction solution and / or
It has been found that the above problems can be solved by removing the aqueous solution of the alkaline earth metal halide salt and separating the precipitated crystals after the reaction, and completed the present invention.

That is, in the production method of the present invention, a substituted or unsubstituted phenol compound is reacted with xylene dihalide to give the following general formula [1]:

[0007]

[Chemical 2] (In the formula, R ¹ and R ² may be the same or different and are selected from the group consisting of hydrogen atom, alkyl group, alkoxy group, halogen atom, aralkyl group, alkyloxycarbonyl group, aryl group and arylsulfonyl group. At least one of m and n may be the same or different and each represents an integer of 1 to 5), and is a substituted or unsubstituted diaryloxymethylbenzene compound. Type phenolic compound, xylene dihalide, and an aqueous alcohol solution, to a mixed solution containing an alkali metal, an alkali metal hydroxide, an alkali metal salt, an alkaline earth metal, an alkaline earth metal hydroxide and an alkaline earth metal. The phenolization by adding a solution containing at least one compound selected from the group consisting of metal salts Alkali metal separated from the reaction solution after the reaction of the compound with the xylene dihalide
And / or remove the aqueous solution of the alkaline earth metal halide salt
Removed by It, it is characterized in that the separation of the resulting diaryl oxymethyl benzene compound from the reaction solution.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described in detail below.

The production method of the present invention comprises adding a mixed solution containing a substituted or non-substituted phenol compound, xylene dihalide and an aqueous alcohol solution to an alkali metal, an alkali metal hydroxide, an alkali metal salt or an alkali. Earth metal, a solution of at least one compound selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal salts is added dropwise to react the phenol compound and the xylene dihalide, the reaction is completed Then separated from the reaction solution
Of alkali metal and / or alkaline earth metal
Removing the aqueous solution of the de-salt is the resultant diaryl oxymethyl benzene compound which separates from the reaction solution.

Here, the phenol compound used in the present invention may be a non-substituted phenol or a compound having a substituent on the benzene ring.
Phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,5-xylenol, o
-Chlorochlorophenol, m-chlorochlorophenol, p-
Chlorolophenol, methoxyphenol, phenylphenol, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, α-naphthol, β-naphthol, 4-phenylsulfonylphenol, 4- (p- Methylphenylsulfonyl) phenol and the like.

The xylene dihalides used in the present invention include o-xylene dichloride and m-
Xylene dichloride, p-xylene dichloride, o
-Xylene dibromide, m-Xylene dibromide, p-
An example is xylene dibromide. The amount of xylene dihalide used is preferably 0.4 to 0.6 mol per mol of the phenol compound. When the amount of xylene dihalide used is less than 0.4 mol, the production amount of the diaryloxymethylbenzene compound tends to decrease, and when it exceeds 0.6 mol, an unknown by-product is formed to produce diaryloxymethylbenzene. The amount of benzene compound produced tends to decrease.

Further, examples of the alcohol used as the solvent in the present invention include methanol, ethanol, isopropyl alcohol and butanol. The amount of the aqueous alcohol solution used is preferably 1.0 to 10 parts by weight with respect to 1 part by weight of the phenol compound. If the amount of the aqueous alcohol solution used is less than 1 part by weight, stirring of the solution will be insufficient, and if it exceeds 10 parts by weight, reaction efficiency and production efficiency will decrease. The alcohol concentration of the aqueous alcohol solution is not particularly limited, but the alcohol concentration is 30% by weight or more and 90% by weight or more.
The following is preferable. When the alcohol concentration is less than the lower limit value, the hydrolysis of xylene dihalide tends to react easily and the purity and yield of the target compound tend to decrease,
When the amount exceeds the upper limit, it tends to be difficult to remove the alkali metal or alkaline earth metal halide salt formed by the reaction from the crystals of the target substance.

The solution containing the alkali metal compound or the alkaline earth metal compound added dropwise to the mixed solvent is an alkali metal, an alkali metal hydroxide, an alkali metal salt, an alkaline earth metal or an alkaline earth metal. It contains a hydroxide or an alkaline earth metal salt, and more specifically, sodium, potassium, lithium, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, carbonic acid. It includes potassium hydrogen, magnesium, magnesium hydroxide, magnesium carbonate, magnesium hydrogen carbonate, calcium, calcium hydroxide, calcium carbonate, calcium hydrogen carbonate and the like. As these alkali metal compounds or alkaline earth metal compounds, one kind of compound may be used alone, or two or more kinds of compounds may be used as a mixture. The solvent of this solution is not particularly limited, but it is preferable to use water; alcohols such as methanol, ethanol, propanol, isopropanol, butanol; or an aqueous solution of the above alcohol, and water or an aqueous alcohol solution of 50% or less is used. It is more preferable to use, and it is most preferable to use water. The content of the alkali metal compound or the alkaline earth metal compound in this solution is preferably 0.8 to 1.3 mol with respect to 1 mol of the phenol compound.
If the amount of these compounds used is less than 0.8 mol, the production amount of the diaryloxymethylbenzene compound tends to decrease, and if it exceeds 1.3 mol, hydrolysis of xylene dihalide proceeds preferentially, As a result, the amount of diaryloxymethylbenzene compound produced tends to decrease. The concentration of the alkali metal compound or the alkaline earth metal compound in the solution is preferably 10 to 70% by weight. If the concentration of the alkali metal compound or the alkaline earth metal compound is less than the lower limit value, the amount of dropping is large and the dropping time is long, so that the process tends to require a lot of time, and if the concentration exceeds the upper limit value, the alkali is exceeded. The metal compound or the alkaline earth metal compound tends to crystallize in the solution and become difficult to drop.

The reaction temperature in the production method of the present invention is not particularly limited, and it can be carried out usually at room temperature to 100 ° C., but a solution containing the alkali metal compound or the alkaline earth metal compound is added dropwise. The reaction temperature at this time is preferably 40 to 85 ° C. If the reaction temperature is lower than 40 ° C, the reaction tends to proceed slowly and the efficiency tends to decrease, and if it exceeds 85 ° C, the hydrolysis of xylene dihalide tends to proceed and the yield of the target compound tends to decrease.

Then, the diaryloxymethylbenzene compound obtained by the above reaction is separated from the reaction solution to obtain the target compound. Here, as a method for separating the diaryloxymethylbenzene compound from the reaction solution,
Examples include filtration and solvent extraction. According to the method of the present invention, the diaryloxymethylbenzene compound can be obtained in high purity, but purification of the separated precipitate by an operation such as recrystallization means that the purity of the obtained diaryloxymethylbenzene compound is high. Is preferable because it tends to be improved.

As described above, according to the manufacturing method of the present invention, the following general formula [1]:

[0017]

[Chemical 3] (In the formula, R ¹ and R ² may be the same or different and are selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen, an aralkyl group, an alkyloxycarbonyl group, an aryl group and an arylsulfonyl group. A diaryloxymethylbenzene compound represented by at least one kind, and m and n may be the same or different and each represents an integer of 1 to 5) can be obtained efficiently and inexpensively by a simple process. . here,
Specific examples of the diaryloxymethylbenzene compound obtained by the method of the present invention include 1,2-diphenoxymethylbenzene, 1,3-diphenoxymethylbenzene, 1,4-diphenoxymethylbenzene, 1,2. −
Di (o-methylphenoxy) methylbenzene, 1,2-
Di (m-methylphenoxy) methylbenzene, 1,2-
Di (p-methylphenoxy) methylbenzene, 1,3-
Di (o-methylphenoxy) methylbenzene, 1,3-
Di (m-methylphenoxy) methylbenzene, 1,3-
Di (p-methylphenoxy) methylbenzene, 1,4-
Di (o-methylphenoxy) methylbenzene, 1,4-
Di (m-methylphenoxy) methylbenzene, 1,4-
Di (p-methylphenoxy) methylbenzene, 1,2-
Di (o-ethylphenoxy) methylbenzene, 1,2-
Di (m-ethylphenoxy) methylbenzene, 1,2-
Di (p-ethylphenoxy) methylbenzene, 1,3-
Di (o-ethylphenoxy) methylbenzene, 1,3-
Di (m-ethylphenoxy) methylbenzene, 1,3-
Di (p-ethylphenoxy) methylbenzene, 1,4-
Di (o-ethylphenoxy) methylbenzene, 1,4-
Di (m-ethylphenoxy) methylbenzene, 1,4-
Di (p-ethylphenoxy) methylbenzene, 1,2-
Di (2,4-dimethylphenoxy) methylbenzene,
1,2-di (2,5-dimethylphenoxy) methylbenzene, 1,2-di (2,6-dimethylphenoxy) methylbenzene, 1,2-di (3,5-dimethylphenoxy) methylbenzene, 1, 3-di (2,4-dimethylphenoxy) methylbenzene, 1,3-di (2,5-dimethylphenoxy) methylbenzene, 1,3-di (2,6)
-Dimethylphenoxy) methylbenzene, 1,3-di (3,5-dimethylphenoxy) methylbenzene, 1,
4-di (2,4-dimethylphenoxy) methylbenzene, 1,4-di (2,5-dimethylphenoxy) methylbenzene, 1,4-di (2,6-dimethylphenoxy)
Methylbenzene, 1,4-di (3,5-dimethylphenoxy) methylbenzene, 1,2-di (o-chlorophenoxy) methylbenzene, 1,2-di (m-chlorophenoxy) methylbenzene, 1,2 -Di (p-chlorophenoxy) methylbenzene, 1,3-di (o-chlorophenoxy) methylbenzene, 1,3-di (m-chlorophenoxy) methylbenzene, 1,3-di (p-chlorophenoxy) Methylbenzene, 1,4-di (o-chlorophenoxy) methylbenzene, 1,4-di (m-chlorophenoxy) methylbenzene, 1,4-di (p-chlorophenoxy) methylbenzene, 1,2-di (O-Methoxyphenoxy) methylbenzene, 1,2-di (m-methoxyphenoxy) methylbenzene, 1,2-di (p-methoxyphenoxy) methyl Benzene, 1,3-di (o-methoxyphenoxy) methylbenzene, 1,3-di (m-methoxyphenoxy) methylbenzene, 1,3-di (p-methoxyphenoxy) methylbenzene, 1,4-di ( o-
Methoxyphenoxy) methylbenzene, 1,4-di (m
-Methoxyphenoxy) methylbenzene, 1,2-di (p-phenylphenoxy) methylbenzene, 1,3-
Di (p-phenylphenoxy) methylbenzene, 1,4
-Di (p-phenylphenoxy) methylbenzene, 1,
2-di (p-methoxycarbonylphenoxy) methylbenzene, 1,3-di (p-methoxycarbonylphenoxy) methylbenzene, 1,4-di (p-methoxycarbonylphenoxy) methylbenzene, 1,2-di (p -Ethoxycarbonylphenoxy) methylbenzene, 1,3
-Di (p-ethoxycarbonylphenoxy) methylbenzene, 1,4-di (p-ethoxycarbonylphenoxy) methylbenzene, 1,2-di (p-benzyloxycarbonylphenoxy) methylbenzene, 1,3-di (p -Benzyloxycarbonylphenoxy) methylbenzene, 1,4-di (p-benzyloxycarbonylphenoxy) methylbenzene, 1,2-di (1-naphthyloxy) methylbenzene, 1,3-di (1-naphthyloxy) Methylbenzene, 1,4-di (1-naphthyloxy) methylbenzene, 1,2-di (2-naphthyloxy) methylbenzene, 1,3-di (2-naphthyloxy) methylbenzene, 1,4-di (2-naphthyloxy) methylbenzene, 1,2-di (4-phenylsulfonylphenoxymethyl) ben Emissions, 1,3-di (4-phenylsulfonyl phenoxymethyl) benzene, 1,4
-Di (4-phenylsulfonylphenoxymethyl) benzene, 1,2-di {4- (p-methylphenylsulfonyl) phenoxymethyl} benzene, 1,3-di4- (p
-Methylphenylsulfonyl) phenoxymethyl} benzene, 1,4-di4- (p-methylphenylsulfonyl) phenoxymethyl} benzene and the like.

[0018]

EXAMPLES The present invention will be described in detail below based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 A 1-liter flask was charged with 164 g of water, 306 g of isopropyl alcohol and 87.5 of o-xylene dichloride.
g, 94 g of phenol, and the temperature of this solution is 70 ° C.
While maintaining at 48%, 66.7% aqueous 48% sodium hydroxide solution
g was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was carried out at 70 ° C. for 1 hour, and the reaction liquid was further heated and reacted under reflux for 3 hours. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals are separated by filtration, dried and 1,2-
Diphenoxymethylbenzene was obtained. The yield of this reaction was 89%. In addition, analysis by liquid chromatography (GULLIVER series manufactured by JASCO Corporation, column: Shim-pack CLC-ODS manufactured by Shimadzu) revealed that the purity of the obtained compound was 96.1%.

Example 2 A 48% aqueous sodium hydroxide solution of Example 1 66.
48% sodium hydroxide aqueous solution 83.3 instead of 7 g
1,2-Diphenoxymethylbenzene was synthesized in the same manner as in Example 1 except that g was used, and the obtained compound was analyzed by liquid chromatography. The yield of the reaction was 92%, and the purity of the obtained compound was 9%.
It was 6.6%.

Example 3 48% aqueous sodium hydroxide solution in Example 1 66.
48% sodium hydroxide aqueous solution 108. instead of 7 g.
In the same manner as in Example 1 except that 3 g was used, 1,2-
Diphenoxymethylbenzene was synthesized, and the obtained compound was analyzed by liquid chromatography. The yield of the reaction was 87%, and the purity of the obtained compound was 95.9.
%Met.

Example 4 87.5 g of o-xylene dichloride in Example 1
1,2-diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography in the same manner as in Example 1 except that 70 g of o-xylene dichloride was used instead of. The yield of the reaction was 88%, and the purity of the obtained compound was 95.7%.

Example 5 87.5 g of o-xylene dichloride in Example 1
1,2-diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography in the same manner as in Example 1 except that 105 g of o-xylene dichloride was used instead of. The yield of the reaction was 89%, and the purity of the obtained compound was 96.3%.

Example 6 The procedure of Example 1 was repeated except that 164 g of water in Example 1 and 66 g of water and 122 g of isopropyl alcohol were used instead of 306 g of isopropyl alcohol.
2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography. 88% yield of reaction
And the purity of the obtained compound was 96.8%.

Example 7 In the same manner as in Example 1 except that water 263 g and isopropyl alcohol 489 g were used instead of water 164 g and isopropyl alcohol 306 g in Example 1.
1,2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography. The reaction yield is 8
9%, and the purity of the obtained compound was 97.5%.

Example 8 The same procedure as in Example 1 was repeated except that instead of 164 g of water and 306 g of isopropyl alcohol in Example 1, 282 g of water and 188 g of isopropyl alcohol were used.
1,2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography. The reaction yield is 8
9%, and the purity of the obtained compound was 95.7%.

Example 9 In the same manner as in Example 1 except that 164 g of water in Example 1 and 71 g of water and 399 g of isopropyl alcohol were used instead of 306 g of isopropyl alcohol,
2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography. 88% yield of reaction
And the purity of the obtained compound was 97.4%.

Example 10 1,2-Diphenoxymethylbenzene was synthesized in the same manner as in Example 1 except that 164 g of water in Example 1 and 141 g of water and 329 g of methanol were used instead of 306 g of isopropyl alcohol. Chromatographic analysis was performed. The yield of the reaction was 87%, and the purity of the obtained compound was 96.0%.

Example 11 Instead of 164 g of water and 306 g of isopropyl alcohol in Example 1, 157 g of water and 31 of butyl alcohol were used.
In the same manner as in Example 1 except that 3 g was used, 1,2-
Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography. The yield of the reaction was 88%, and the purity of the obtained compound was 96.2%.

Example 12 1,3-diphenoxymethylbenzene was synthesized in the same manner as in Example 1 except that m-xylene dichloride was used in place of o-xylene dichloride, and liquid chromatography was used. Analysis was carried out. The yield of the reaction was 93%, and the purity of the obtained compound was 9
It was 6.4%.

Example 13 1,4-diphenoxymethylbenzene was synthesized in the same manner as in Example 1 except that p-xylenedichloride was used in place of o-xylenedichloride, and liquid chromatography was used. Analysis was carried out. The yield of the reaction was 91%, and the purity of the obtained compound was 9%.
It was 7.1%.

Example 14 A 1-liter flask was charged with 189 g of water, 351 g of isopropyl alcohol and 87.5 m-xylene dichloride.
g, p-cresol 108 g, and the temperature of this solution is 7
48% sodium hydroxide aqueous solution 8 while maintaining at 0 ° C
3.3 g was added dropwise over 1 hour. After dropping, 7
The reaction was carried out at 0 ° C. for 1 hour, the temperature of the reaction solution was further raised, and the reaction was carried out under reflux for 3 hours. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals were separated by filtration and dried to obtain 1,2-di (p-methylphenoxymethyl) benzene. The yield of this reaction was 90%. In addition, Example 1
When analyzed by liquid chromatography in the same manner as in 1., the purity of the obtained compound was 96.8%.

Example 15 In a 1-liter flask, 225 g of water, 418 g of isopropyl alcohol, and 87.5 m-xylene dichloride.
g and p-chlorophenol 128.5 g were added, and while maintaining the temperature of this solution at 70 ° C., 83.3 g of 48% aqueous sodium hydroxide solution was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was carried out at 70 ° C. for 1 hour, and the reaction liquid was further heated and reacted under reflux for 3 hours. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals are separated by filtration,
It was dried to obtain 1,3-di (p-chlorophenoxymethyl) benzene. The yield of this reaction was 91%. Also,
When liquid chromatographic analysis was performed in the same manner as in Example 1, the purity of the obtained compound was 96.6%.
Met.

Example 16 In a 1 liter flask, 214 g of water, 397 g of isopropyl alcohol, and 87.5 of p-xylene dichloride.
g, 2,6-xylenol (122 g) was added, and while this solution was maintained at 70 ° C., a 48% sodium hydroxide aqueous solution 8
3.3 g was added dropwise over 1 hour. After dropping, 7
The reaction was carried out at 0 ° C. for 1 hour, the temperature of the reaction solution was further raised, and the reaction was carried out under reflux for 3 hours. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals were separated by filtration and dried to obtain 1,4-di (2,6-dimethylphenoxymethyl) benzene. The yield of this reaction was 90%. Also,
When analyzed by liquid chromagraphy in the same manner as in Example 1, the purity of the obtained compound was 96.9%.
Met.

Example 17 A 1-liter flask was charged with 298 g of water, 553 g of isopropyl alcohol and 87.5 of p-xylylene dichloride.
g and 170 g of p-phenylphenol were added, and while maintaining this solution at 70 ° C., 83.3 g of a 48% sodium hydroxide aqueous solution was added dropwise over 1 hour. After the dropping is completed,
The reaction was carried out at 70 ° C. for 1 hour, the temperature of the reaction solution was further raised, and the reaction was carried out under reflux for 3 hours. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals were separated by filtration and dried to obtain 1,4-di (p-phenylphenoxymethyl) benzene. The yield of this reaction was 89%. Further, when the analysis by liquid chromatography was performed in the same manner as in Example 1, the purity of the obtained compound was 96.2%.

Example 18 In a 1-liter flask, 259 g of water, 481 g of isopropyl alcohol, 3 go-xylene dichloride 87.
5 g and 148 g of β-naphthol were added, and this solution was added to 70
48% sodium hydroxide aqueous solution 83.
3 g was added dropwise over 1 hour. After the dropping, 70 ℃
Was reacted for 1 hour, and the temperature of the reaction solution was further raised to allow reaction for 3 hours under reflux. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals are separated by filtration, dried and then 1,2
-Di (β-naphthyloxymethyl) benzene was obtained. The yield of this reaction was 88%. Further, when the analysis by liquid chromatography was performed in the same manner as in Example 1, the purity of the obtained compound was 96.7%.

Example 19 In a 1-liter flask, 340 g of water, 631 g of isopropyl alcohol, and 87.5 of p-xylene dichloride.
g, 194 g of butyl p-hydroxybenzoate were added, and while maintaining this solution at 70 ° C., 83.3 g of a 48% aqueous sodium hydroxide solution was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was carried out at 70 ° C. for 1 hour, and the reaction liquid was further heated and reacted under reflux for 3 hours. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals were separated by filtration and dried to obtain 1,4-di {4- (p-butyloxycarbonylphenoxy) methyl} benzene. The yield of this reaction was 88%. Further, when the analysis by liquid chromatography was performed in the same manner as in Example 1, the purity of the obtained compound was 96.7%.

Example 20 In a 1-liter flask, 410 g of water, 761 g of isopropyl alcohol, and 87.5 of o-xylene dichloride.
g, 234 g of 4-phenylsulfonylphenol,
While maintaining this solution at 70 ° C., 83.3 g of a 48% aqueous sodium hydroxide solution was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was carried out at 70 ° C. for 1 hour, and the reaction liquid was further heated and reacted under reflux for 3 hours. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals are separated by filtration,
It was dried to obtain 1,2-di (4-phenylsulfonylphenoxymethyl) benzene. The yield of this reaction was 91%. Moreover, when the analysis by liquid chromatography was performed in the same manner as in Example 1, the purity of the obtained compound was 96.5%.

Example 21 48% aqueous sodium hydroxide solution in Example 1 66.
1,2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography in the same manner as in Example 1 except that 112 g of a 50% aqueous potassium hydroxide solution was used instead of 7 g. The yield of the reaction was 92%, and the purity of the obtained compound was 96.9%.

Example 22 In a 1 liter flask, water 164 g, isopropyl alcohol 306 g, o-xylene dichloride 87.5
g, 94 g of phenol, and the temperature of this solution is 70 ° C.
48% sodium hydroxide aqueous solution 58.3 while maintaining
g was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was carried out at 70 ° C. for 1 hour, and the reaction liquid was further heated and reacted under reflux for 3 hours. After completion of the reaction, the sodium chloride aqueous solution separated from the reaction solution was removed, and the reaction solution was cooled to precipitate crystals. The crystals are separated by filtration, dried and 1,2-
Diphenoxymethylbenzene was obtained. The yield of this reaction was 83%. Further, when the analysis by liquid chromatography was performed in the same manner as in Example 1, the purity of the obtained compound was 95.0%.

Example 23 48% aqueous sodium hydroxide solution 5 in Example 22
48% aqueous sodium hydroxide solution 11 instead of 8.3 g
Example 22 was repeated except that 6.7g was used.
1,2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography. The reaction yield is 7
9%, and the purity of the obtained compound was 81.4%.

Example 24 o-Xylene dichloride 87.5 in Example 22
1,2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography in the same manner as in Example 22 except that 61.8 g of o-xylenedichloride was used instead of g. The yield of the reaction was 82%, and the purity of the obtained compound was 95.1%.

Example 25 o-xylene dichloride 87.5 in Example 22
1,2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography in the same manner as in Example 22 except that 113.8 g of o-xylene dichloride was used instead of g. The yield of the reaction is 74%,
The purity of the obtained compound was 94.7%.

Example 26 The same procedure as in Example 22 was carried out except that 26 g of water and 49 g of isopropyl alcohol were used instead of 164 g of water and 306 g of isopropyl alcohol in Example 22.
1,2-Diphenoxymethylbenzene was synthesized and analyzed by liquid chromatography. The reaction yield is 8
2%, and the purity of the obtained compound was 94.6%.

Example 27 1,2-diphenoxymethylbenzene was synthesized in the same manner as in Example 22 except that 164 g of water in Example 22 and 395 g of water and 733 g of isopropyl alcohol were used instead of 306 g of isopropyl alcohol. Analysis by liquid chromatography was performed. The yield of the reaction was 73%, and the purity of the obtained compound was 97.5%.

Comparative Example 1 1,2-Diphenoxymethylbenzene was synthesized in the same manner as in Example 22 except that 164 g of water in Example 22 and 470 g of water in place of 306 g of isopropyl alcohol were used, and liquid chromatography was performed. Analysis was carried out. The yield of the reaction was 79%, and the purity of the obtained compound was 75.4%.

For each of Examples 1 to 27 and Comparative Example 1 described above, the types of the substituents R ¹ and R ² in the above formula [1], the substitution position of the halogen atom of xylene halide, and the molar ratio of xylene halide to the phenol compound. , Type of alkali compound and molar ratio to phenol compound, type of solvent and weight ratio to phenol compound,
Table 1 shows the yield of the reaction and the purity of the obtained compound.
In addition, in Table 1, R ¹ and R ² of the unsubstituted compound are described as H (hydrogen atom). Further, in the solvent type column of Table 1, IP
A represents isopropyl alcohol.

[0048]

[Table 1]

[0049]

As described above, according to the production method of the present invention, a highly pure diaryloxymethylbenzene compound can be obtained with a high yield in a simple process. Therefore, by using this method, the diaryloxymethylbenzene compound can be efficiently produced at a low cost in a simple process.

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Claims (2)

(57) [Claims] 1. A substituted or unsubstituted phenol compound and xylene dihalide are reacted to react with the following general formula [1]: (In the formula, R ¹ and R ² may be the same or different and are selected from the group consisting of hydrogen atom, alkyl group, alkoxy group, halogen atom, aralkyl group, alkyloxycarbonyl group, aryl group and arylsulfonyl group. At least one of m and n may be the same or different and each represents an integer of 1 to 5), and a substituted or unsubstituted diaryloxymethylbenzene compound Type phenolic compound, xylene dihalide, and an aqueous alcohol solution, to a mixed solution containing an alkali metal, an alkali metal hydroxide, an alkali metal salt, an alkaline earth metal, an alkaline earth metal hydroxide and an alkaline earth metal. The phenol by adding a solution containing at least one compound selected from the group consisting of metal salts The the compound and the xylene dihalide is reacted, the reaction completion
Then, the alkali metal and / or alkali separated from the reaction solution
A method for producing a diaryloxymethylbenzene compound, which comprises removing an aqueous solution of a halide salt of a rare earth metal and separating the obtained diaryloxymethylbenzene compound from the reaction solution. 2. The mixed solution comprises a substituted or unsubstituted phenol compound, 0.4 to 0.6 mol of xylene dihalide per 1 mol of the phenol compound, and 1 part by weight of the phenol compound. 1.0 to 10 parts by weight of an alcohol aqueous solution, and 0.8 to 1.3 mol of an alkali metal, an alkali metal hydroxide or an alkali metal salt with respect to 1 mol of the phenol compound. A solution containing at least one compound selected from the group consisting of an alkaline earth metal, a hydroxide of an alkaline earth metal, and an alkaline earth metal salt is added dropwise to the mixed solution. The manufacturing method described.