JP4520591B2 - Method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone - Google Patents

Description

【００１３】
第１表に見られるように、４,４'−ジアリルオキシジフェニルスルホン中に含有されるアルカリ総量が５〜４５ppm（重量比）である実施例１〜４においては、精製品の収率が高く、３,３'−ジアリル−４,４'−ジヒドロキシジフェニルスルホンの含有量が多く、５−(３−アリル−４−ヒドロキシ)フェニルスルホニル−１−オキサ−２−メチルインダンの含有量が少なく、純度が高い。また、アルカリ総量が少ないほど、精製品収率、純度ともに高くなっている。これに対して、４,４'−ジアリルオキシジフェニルスルホン中に含有されるアルカリ総量が６０〜１００ppm（重量比）である比較例１〜２においては、精製品の収率、純度がともに低い。
【００１４】
【発明の効果】
本発明方法によれば、地肌カブリ成分が少なく純度の高い３,３'−ジアリル−４,４'−ジヒドロキシジフェニルスルホンを高収率で製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone. More specifically, the present invention can provide 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone useful as a color developer for heat-sensitive recording materials with a low background fog component and a high yield. , 3'-diallyl-4,4'-dihydroxydiphenyl sulfone.
[0002]
[Prior art]
3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone is a substance useful as a color developer for heat-sensitive recording materials, and various production methods have been attempted. For example, JP-A-61-89090 and JP-A-62-53957 disclose 3-allyl-4 as a method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone with less fog. -Hydroxy-4'-allyloxydiphenylsulfone is 5 to 20% by weight of 4,4'-diallyloxydiphenylsulfone, and the yield of 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone is 90% by weight. A method for terminating the heat transfer reaction while suppressing the following has been proposed. The reaction mixture is extracted with an alkali solution, acidified, and then recrystallized and purified by a mixed solvent of a dichloroalkane solvent, an aromatic solvent, an alcohol solvent or a glycol solvent, to obtain 3,3′-diallyl- 4,4′-Dihydroxydiphenylsulfone is obtained.
Japanese Patent Laid-Open No. 11-29549 discloses a DSC (Te) of 149 ° C. or higher as a heat-sensitive recording material having high sensitivity, little background fogging during wet heat, and excellent image storability. In the powder X-ray diffraction method, it is a crystal form characterized by an X-ray diffraction pattern having peaks at least at diffraction angles (2θ) [°] 7.2 and 22.0, and 3,3′-diallyl-4,4 There has been proposed a heat-sensitive recording material containing crystals having a content of '-dihydroxydiphenylsulfone of 96% by weight or more. 4,4′-diallyloxydiphenylsulfone is heated and rearranged in an inert water-insoluble organic solvent having a high boiling point, and the amount of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone produced is 89 to 93% by weight. After completion of the reaction, extraction with an aqueous alkali solution and purification using activated carbon to a solution partially neutralized with an acid, followed by precipitation into an aqueous acid solution to precipitate crystals, or after extraction with an aqueous alkali solution 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone is obtained by adding water and a water-insoluble organic solvent, separating the aqueous layer and the oil layer, and adding an aqueous acid solution to the aqueous layer.
5- (3-Allyl-4-hydroxy) phenylsulfonyl-1-generated by a thermal rearrangement reaction in 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone used as a developer of a heat-sensitive recording material If there are many by-products such as oxa-2-methylindane, 3-allyl-4-hydroxy-4′-allyloxydiphenylsulfone, 3-allyl-4,4′-dihydroxydiphenylsulfone, the background fogging becomes intense. Become. In the production method described above, since there are many background fog components produced as a by-product during the rearrangement reaction, the removal of the background fog is insufficient and the background fog components are generated, or even if the background fog components can be sufficiently removed. The rate is low, and there is a difficulty as an inexpensive and industrially produced method. Therefore, there has been a demand for a method for economically producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone having a high purity and a low background fog component.
[0003]
[Problems to be solved by the invention]
In the present invention, 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone useful as a developer for a heat-sensitive recording material can be obtained in a high yield with little background fog component. The object of the present invention is to provide a method for producing diallyl-4,4′-dihydroxydiphenylsulfone.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have calculated that the total amount of alkali contained in 4,4′-diallyloxydiphenylsulfone is 50 ppm (weight ratio) or less in terms of sodium hydroxide. It was found that high-purity 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone can be obtained in a high yield by carrying out a thermal rearrangement reaction as follows, and the present invention was completed based on this finding. It came to do.
That is, the present invention
(1) Purification of 4,4′-diallyloxydiphenylsulfone in a process for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone by heat rearrangement reaction of 4,4′-diallyloxydiphenylsulfone The total amount of alkali contained in the 4,4′-diallyloxydiphenylsulfone is 50 ppm (weight ratio) or less in terms of sodium hydroxide, and the heat rearrangement reaction is performed. A process for producing diallyl-4,4′-dihydroxydiphenylsulfone , and
(2) 4,4′-diallyloxydiphenylsulfone is purified by washing the crystal obtained by reacting 4,4′-dihydroxydiphenylsulfone and allyl halide in an organic solvent in the presence of alkali with water. A process for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone according to (1),
Is to provide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone according to the present invention, 3,4′-diallyloxydiphenylsulfone is subjected to a thermal rearrangement reaction to produce 3,3′-diallyl-4,4 ′. -In the method for producing dihydroxydiphenyl sulfone, the total amount of alkali contained in 4,4'-diallyloxydiphenyl sulfone is reduced to 50 ppm (weight ratio) or less in terms of sodium hydroxide and subjected to a heat rearrangement reaction.
In the method of the present invention, 4,4′-diallyloxydiphenylsulfone used as a raw material for 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone is obtained by combining 4,4′-dihydroxydiphenylsulfone and allyl halide with an organic solvent. It is produced by a dehydrohalogenation reaction in the presence of an alkali such as an alkali metal hydroxide, an alkaline earth metal hydroxide or a carbonate. Therefore, in 4,4′-diallyloxydiphenylsulfone, alkali metal hydroxide, alkaline earth metal hydroxide, carbonate, halide, alkali metal salt of 4,4′-dihydroxydiphenylsulfone, Impurities such as alkaline earth metal salts of 4,4′-dihydroxydiphenylsulfone, alkali metal salts of 4-allyloxy-4′-hydroxydiphenylsulfone, and alkaline earth metal salts of 4-allyloxy-4′-hydroxydiphenylsulfone Mixing is inevitable. The total amount of these impurities can be quantified as an alkali component.
[0006]
In the method of the present invention, the total amount of alkali contained in 4,4′-diallyloxydiphenylsulfone is 50 ppm (weight ratio) or less in terms of sodium hydroxide, and the heat rearrangement reaction is performed. The total amount of alkali contained in 4,4′-diallyloxydiphenylsulfone is obtained by dissolving 4,4′-diallyloxydiphenylsulfone in an organic solvent such as dimethylsulfoxide, adding an aqueous sodium hydroxide solution, and then using hydrochloric acid. The total amount of alkali contained can be calculated by converting it to sodium hydroxide as compared with the blank.
There is no particular limitation on the method in which the total amount of alkali contained in 4,4′-diallyloxydiphenylsulfone used as a raw material is 50 ppm (weight ratio) or less in terms of sodium hydroxide, for example, 4,4′- Crystals obtained by reacting dihydroxydiphenylsulfone and allyl chloride in an organic solvent in the presence of an alkali are filtered and washed to obtain wet 4,4′-diallyloxydiphenylsulfone crystals. Next, wet 4,4′-diallyloxydiphenylsulfone crystal and warm water are put into a reaction kettle or a mixing kettle, and after stirring and mixing at 40 to 80 ° C., filtration, washing, and drying are performed, so that the total amount of alkali contained is reduced. 4,4′-diallyloxydiphenyl sulfone having a concentration of 50 ppm (weight ratio) or less can be obtained.
[0007]
When 4,4'-diallyloxydiphenylsulfone containing a total amount of alkali converted to sodium hydroxide exceeds 50 ppm (weight ratio) by heat rearrangement reaction, alkali metal hydroxide, alkaline earth metal hydroxide, carbonate , Halide, alkali metal salt of 4,4′-dihydroxydiphenylsulfone, alkaline earth metal salt of 4,4′-dihydroxydiphenylsulfone, alkali metal salt of 4-allyloxy-4′-hydroxydiphenylsulfone, 4-allyloxy Alkaline earth metal salts of -4'-hydroxydiphenylsulfone coordinate with phenolic hydroxyl groups generated by ether-bonded oxygen and rearrangement reactions, and promote side reactions by forming complexes and salts. By-products including fog components are thought to be produced, but the detailed mechanism is unknown. .
When the total alkali content exceeds 50 ppm (weight ratio), 5- (3-allyl-4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane and 3-allyl-4-hydroxy, which are background fog components Formation of 4'-allyloxydiphenylsulfone, 3-allyl-4,4'-dihydroxydiphenylsulfone, etc. is promoted, and by-product reaction from 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone Is generated, which makes purification difficult and causes a decrease in the purity of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone, generation of background fog components, and a decrease in yield for removing background fog components.
[0008]
Examples of alkali metal hydroxides contained in 4,4′-diallyloxydiphenylsulfone include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include magnesium hydroxide and water. There are calcium oxides, and carbonates include sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, etc., and halides include sodium chloride, potassium chloride, calcium chloride, magnesium chloride. Sodium bromide, potassium bromide, calcium bromide, magnesium bromide and the like.
In the method of the present invention, the thermal rearrangement reaction of 4,4′-diallyloxydiphenylsulfone is carried out without solvent or in an inert water-insoluble organic solvent such as an aliphatic hydrocarbon solvent or an aromatic organic solvent having a high boiling point. , By heating to 190-220 ° C. After completion of the reaction, the reaction mixture is purified by operations such as alkali extraction, solvent extraction, washing, acid precipitation, recrystallization and the like, and 3,3′-diallyl-4, which has excellent performance as a color developer for heat-sensitive recording materials. 4'-dihydroxydiphenyl sulfone can be obtained.
[0009]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the examples and comparative examples, the total alkali content was determined as follows. That is, 30 g of 4,4′-diallyloxydiphenyl sulfone was dissolved in 450 g of dimethyl sulfoxide, 10 mL of 1/50 mol / L sodium hydroxide aqueous solution was added, and titrated with 1/100 mol / L hydrochloric acid. Compared with the value when titrated without adding 4,4'-diallyloxydiphenylsulfone, the total alkali content was converted to sodium hydroxide.
Example 1
In a four-necked flask, 413 g of 4,4′-diallyloxydiphenylsulfone having a total alkali content converted to sodium hydroxide of 5 ppm (weight ratio), 275 g of Diana Fresia W-8 [Idemitsu Kosan Co., Ltd.] and kerosene [Large Kyo Petroleum Co., Ltd.] was charged with 275 g and subjected to a heat rearrangement reaction at 205 to 210 ° C. for 7 hours under a nitrogen stream.
The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone (hereinafter abbreviated as di-rearranged) 91.3%, 5- (3- Allyl-4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane (hereinafter abbreviated as indane) 1.8%, 3-allyl-4-hydroxy-4′-allyloxydiphenylsulfone (hereinafter mono) It was abbreviated as a rearranged product.) 2.9% and 3-allyl-4,4′-dihydroxydiphenylsulfone (hereinafter abbreviated as a monoallyl product) 1.1%.
The reaction mixture was cooled, 715 g of a 13 wt% aqueous sodium hydroxide solution was added, and the mixture was allowed to stand. After that, a lower neck alkaline aqueous solution and 39 g of activated carbon were charged into a four-necked flask and decolorized at 80 ° C. for 1 hour. The activated carbon was filtered off. Further, a decolorization treatment solution was charged into a four-necked flask, and 184 g of 50% by weight sulfuric acid was added dropwise at 60 ° C. for acid precipitation, and the precipitated crystals were separated by filtration. Crystals separated by filtration in a four-necked flask and 780 g of ethane dichloride were charged, 9.4 g of isopropanol was added and heated to reflux, and then cooled to 25 ° C. The precipitated crystals were filtered, washed with 300 g of ethane dichloride, and then dried to obtain 293 g of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product. The obtained 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product had a HPLC composition ratio (area percentage) of 96.2% di-rearranged product and 0.3% indane product.
Example 2
Instead of 4,4′-diallyloxydiphenylsulfone having a total alkali content of 5 ppm (weight ratio) used in Example 1, 4,4′-diallyloxydiphenylsulfone having a total alkali content of 15 ppm (weight ratio) was used. The reaction was performed in the same manner as in Example 1 except that. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was di-rearranged 91.0%, indane 1.9%, mono-rearranged 3.2%, and monoallyl 0.9%.
Furthermore, by treating in the same manner as in Example 1, 289 g of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product was obtained. The obtained 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product had a HPLC composition ratio (area percentage) of 96.1% di-rearranged product and 0.4% indane product.
[0010]
Example 3
Instead of 4,4′-diallyloxydiphenylsulfone having a total alkali content of 5 ppm (weight ratio) used in Example 1, 4,4′-diallyloxydiphenylsulfone having a total alkali content of 30 ppm (weight ratio) was used. The reaction was performed in the same manner as in Example 1 except that. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was 90.7% di-rearranged, 2.4% indane, 3.0% mono-rearranged, and 1.0% monoallyl.
Furthermore, by treating in the same manner as in Example 1, 281 g of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product was obtained. The obtained 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product had a HPLC composition ratio (area percentage) of 96.0% di-rearranged product and 0.4% indane product.
Example 4
Instead of 4,4′-diallyloxydiphenylsulfone having a total alkali content of 5 ppm (weight ratio) used in Example 1, 4,4′-diallyloxydiphenylsulfone having a total alkali content of 45 ppm (weight ratio) was used. The reaction was performed in the same manner as in Example 1 except that. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was 89.8% di-rearranged, 2.9% indane, 2.8% mono-rearranged, and 0.9% monoallyl.
Further, by treating in the same manner as in Example 1, 277 g of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product was obtained. The obtained 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product had a HPLC composition ratio (area percentage) of 95.9% di-rearranged product and 0.5% indane product.
[0011]
Comparative Example 1
In a four-necked flask, 413 g of 4,4′-diallyloxydiphenylsulfone having a total alkali content converted to sodium hydroxide of 60 ppm (weight ratio), 275 g of Diana Fresia W-8 [Idemitsu Kosan Co., Ltd.] and kerosene [large Kyo Petroleum Co., Ltd.] was charged with 275 g and subjected to a heat rearrangement reaction at 205 to 210 ° C. for 7 hours under a nitrogen stream. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was 87.8% di-rearranged, 4.8% indane, 3.2% mono-rearranged, and 1.4% mono-allyl.
The reaction mixture was cooled, 715 g of a 13 wt% aqueous sodium hydroxide solution was added, and the mixture was allowed to stand. After that, a lower neck alkaline aqueous solution and 39 g of activated carbon were charged into a four-necked flask and decolorized at 80 ° C. for 1 hour. The activated carbon was filtered off. A decolorization treatment solution was charged into a four-necked flask, and 184 g of 50% by weight sulfuric acid was added dropwise at 60 ° C. for acid precipitation, and the precipitated crystals were separated by filtration. Crystals separated by filtration in a four-necked flask and 780 g of ethane dichloride were charged, 9.4 g of isopropanol was added and heated to reflux, and then cooled to 25 ° C. The precipitated crystals were separated by filtration, washed with 300 g of ethane dichloride, and then dried to obtain 248 g of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product. The obtained 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product had a HPLC composition ratio (area percentage) of 92.2% di-rearranged product and 1.6% indane product.
Comparative Example 2
Instead of 4,4′-diallyloxydiphenylsulfone having a total alkali content of 5 ppm (weight ratio) used in Comparative Example 1, 4,4′-diallyloxydiphenylsulfone having a total alkali content of 100 ppm (weight ratio) was used. The reaction was performed in the same manner as in Comparative Example 1 except that. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was di-rearranged body 86.9%, indane body 6.2%, mono-rearranged body 3.1%, and monoallyl body 1.5%.
Further, by performing the same treatment as in Example 1, 235 g of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product was obtained. The obtained 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product had a HPLC composition ratio (area percentage) of 93.0% di-rearranged product and 1.8% indane product.
The results of Examples 1-4 and Comparative Examples 1-2 are shown in Table 1.
[0012]
[Table 1]

[0013]
As can be seen from Table 1, in Examples 1 to 4, where the total amount of alkali contained in 4,4′-diallyloxydiphenylsulfone is 5 to 45 ppm (weight ratio), the yield of the purified product is high. High content of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone, low content of 5- (3-allyl-4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane, High purity. Further, the smaller the total amount of alkali, the higher the purified product yield and purity. In contrast, in Comparative Examples 1 and 2 in which the total amount of alkali contained in 4,4′-diallyloxydiphenyl sulfone is 60 to 100 ppm (weight ratio), the yield and purity of the purified product are both low.
[0014]
【The invention's effect】
According to the method of the present invention, 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone having a low background fog component and high purity can be produced in a high yield.

Claims (2)

In a method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone by subjecting 4,4′-diallyloxydiphenylsulfone to a rearrangement reaction by heating, 4,4′-diallyloxydiphenylsulfone is purified, 3,3′-diallyl-4, characterized in that the total amount of alkali contained in the 4,4′-diallyloxydiphenylsulfone is 50 ppm (weight ratio) or less in terms of sodium hydroxide and undergoes a heat rearrangement reaction. , 4′-Dihydroxydiphenylsulfone production method. The 4,4'-diallyloxydiphenyl sulfone is purified by washing with water the crystals obtained by reacting 4,4'-dihydroxydiphenyl sulfone and allyl halide in an organic solvent in the presence of alkali. Of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone.