JP2002030065A - Method for producing 3,3'-diallyl-4,4'- dihydroxydiphenylsulfone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing 3,3'-diallyl-4,4'- dihydroxydiphenylsulfone, by which the 3,3'-diallyl1-4,4'-dihydroxydiphenylsulfone useful as a developing agent for heat-sensitive recording materials and scarcely containing components causing halation on the surfaces of substrates can be obtained in a high yield. SOLUTION: This method for producing 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone by subjecting 4,4'-diallyloxydiphenylsulfone to a thermal rearrangement reaction, is characterized by subjecting the 4,4'-diallyloxydiphenylsulfone to the thermal rearrangement reaction, while controlling the total amount of alkalis contained in the 4,4'-diallyloxydiphenylsulfone to <=500 ppm (weight ratio) in terms of sodium hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone. More specifically, the present invention provides 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone, which is useful as a developer for a thermosensitive recording material, with a low background fog component and a high yield. , 3'-diallyl-4,
The present invention relates to a method for producing 4′-dihydroxydiphenyl sulfone.

[0002]

2. Description of the Related Art 3,3'-Diallyl-4,4'-dihydroxydiphenyl sulfone is a useful substance as a developer for heat-sensitive recording materials, and various production methods have been tried. For example, JP-A-61-89090 and JP-A-6-89090
JP-A-2-53957 discloses a method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone having a low fog, by using 3-allyl-4-hydroxy-4′-allyloxydiphenylsulfone. 3,5 ′-% by weight of '-diallyloxydiphenyl sulfone
A method has been proposed in which the rate of formation of diallyl-4,4'-dihydroxydiphenyl sulfone is suppressed to 90% by weight or less to terminate the heat transfer reaction. The reaction mixture was extracted with an alkali solution and subjected to acid precipitation, and then recrystallized and purified with a mixed solvent of a dichloroalkane-based solvent, an aromatic-based solvent, and an alcohol-based or glycol-based solvent to obtain 3,3'-diallyl-. Four,
4'-Dihydroxydiphenyl sulfone is obtained. Japanese Patent Application Laid-Open No. 11-29549 discloses that a heat-sensitive recording material having high sensitivity, little fog on the surface when wet and having excellent image storability has a DSC (Te) of 149 ° C. or higher,
In powder X-ray diffraction using u-Kα ray, X having peaks at least at diffraction angles (2θ) [゜] 7.2 and 22.0.
Crystal form characterized by X-ray diffraction
A heat-sensitive recording material containing crystals having a diallyl-4,4'-dihydroxydiphenylsulfone content of 96% by weight or more has been proposed. 4,4'-Diallyloxydiphenyl sulfone is heated and rearranged in a high boiling inert water-insoluble organic solvent, and the amount of 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone produced is 89 to 93% by weight. After completion of the reaction and extraction with an aqueous alkali solution, the solution partially neutralized with an acid is purified using activated carbon, and then introduced into an aqueous acid solution to precipitate crystals, or after extraction with an aqueous alkali solution. , Water and a water-insoluble organic solvent, and the aqueous layer and the oil layer are separated.
3′-Diallyl-4,4′-dihydroxydiphenyl sulfone is obtained. In 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone used as a developer of a thermosensitive recording material, 5- (3-allyl-4-hydroxy) phenylsulfonyl-1- formed by a heat rearrangement reaction. Oxa-2-methylindane, 3-allyl-4-hydroxy-
4'-allyloxydiphenyl sulfone, 3-allyl-
When a large amount of by-products such as 4,4'-dihydroxydiphenyl sulfone is contained, background fog becomes severe. In the above-described production method, since there are many background fog components by-produced at the time of the rearrangement reaction, the removal of the background fog is insufficient and the background fog is generated. The rate is low, and there is a drawback as an inexpensive and industrial production method. Therefore, there has been a demand for a method of economically producing 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone having high purity and low background fog components.

[0003]

SUMMARY OF THE INVENTION The present invention provides 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone, which is useful as a developer for heat-sensitive recording materials, with a low background fog component and high yield. 3,3′-diallyl- which can be obtained
The object of the present invention is to provide a method for producing 4,4'-dihydroxydiphenyl sulfone.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the total amount of alkali contained in 4,4′-diallyloxydiphenyl sulfone was converted to sodium hydroxide. By performing a heat transfer reaction at a converted value of 50 ppm (weight ratio) or less, high purity 3,3
3′-diallyl-4,4′-dihydroxydiphenyl sulfone was found to be obtained in high yield,
Based on this finding, the present invention has been completed. That is, in the present invention, 4,3′-diallyloxydiphenyl sulfone is subjected to a heat rearrangement reaction to give 3,3′-diallyl-4,4′-.
The method for producing dihydroxydiphenyl sulfone is characterized in that 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 the heat rearrangement reaction is carried out. It is intended to provide a method for producing 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The 3,3'-diallyl-4,
In the method for producing 4′-dihydroxydiphenyl sulfone, a method for producing 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone by subjecting 4,4′-diallyloxydiphenyl sulfone to a heat rearrangement reaction,
The total amount of alkali contained in 4,4′-diallyloxydiphenyl sulfone was converted to sodium hydroxide by 50%.
A heat rearrangement reaction is performed at a ppm (weight ratio) or less. In the method of the present invention, 4,4'-diallyloxydiphenylsulfone, which is a raw material for 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone, comprises 4,4'-dihydroxydiphenylsulfone and allyl halide, and 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, 4,
In 4′-diallyloxydiphenyl sulfone, hydroxides of alkali metals, hydroxides, carbonates and halides of alkaline earth metals, alkali metal salts of 4,4′-dihydroxydiphenyl sulfone, 4,4 ′ -The contamination of impurities such as alkaline earth metal salts of dihydroxydiphenylsulfone, alkaline metal salts of 4-allyloxy-4'-hydroxydiphenylsulfone and alkaline earth metal salts of 4-allyloxy-4'-hydroxydiphenylsulfone is avoided. Absent. All of these impurities can be quantified as alkaline components in total.

In the method of the present invention, the total amount of alkali contained in 4,4'-diallyloxydiphenylsulfone is reduced to 50 ppm (weight ratio) or less in terms of sodium hydroxide to carry out a heat rearrangement reaction. The total amount of alkali contained in 4,4′-diallyloxydiphenyl sulfone was 4,4′-diallyloxydiphenyl sulfone.
Dissolve 4'-diallyloxydiphenyl sulfone in an organic solvent such as dimethyl sulfoxide, add an aqueous solution of sodium hydroxide, titrate with hydrochloric acid, and compare with a blank to convert the total alkali content to sodium hydroxide. Can be obtained by: The total amount of alkali contained in 4,4'-diallyloxydiphenyl sulfone as a raw material is calculated as 50% in terms of sodium hydroxide.
There is no particular limitation on the method of reducing the concentration to below ppm (weight ratio). For example, crystals obtained by reacting 4,4′-dihydroxydiphenylsulfone and allyl chloride in an organic solvent in the presence of an alkali are filtered and washed. A wet 4,4'-diallyloxydiphenyl sulfone crystal is obtained. Next, the wet 4,4′-diallyloxydiphenylsulfone crystal and warm water are put into a reaction vessel or a mixing vessel, and the mixture is stirred and mixed at 40 to 80 ° C., and then filtered, washed, and dried, so that the total amount of alkali contained is reduced. 4,4′-Diallyloxydiphenyl sulfone having a concentration of 50 ppm or less (weight ratio) can be obtained.

When 4,4'-diallyloxydiphenylsulfone having a total alkali content in terms of sodium hydroxide exceeding 50 ppm (weight ratio) is subjected to a heat rearrangement reaction, an alkali metal hydroxide or an alkaline earth metal hydroxide is obtained. An alkali metal salt of 4,4′-dihydroxydiphenylsulfone, an alkali earth metal salt of 4,4′-dihydroxydiphenylsulfone, an alkali metal salt of 4-allyloxy-4′-hydroxydiphenylsulfone, Alkaline earth metal salts of 4-allyloxy-4'-hydroxydiphenylsulfone, etc., promote side reactions by coordinating to oxygen of ether bond or phenolic hydroxyl group generated by rearrangement reaction, or forming complex or salt. Is thought to produce by-products such as background fog It is unknown. When the total amount of the contained alkalis exceeds 50 ppm (weight ratio), 5- (3-allyl-4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane, which is a background fog component,
The formation of allyl-4-hydroxy-4'-allyloxydiphenylsulfone, 3-allyl-4,4'-dihydroxydiphenylsulfone and the like is promoted, and 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone is promoted. A purification reaction becomes difficult due to a by-product reaction from the 3,3′-
This causes a decrease in the purity of diallyl-4,4'-dihydroxydiphenyl sulfone, generation of a background fog component, and a decrease in the yield for removing the background fog component.

The alkali metal hydroxide contained in 4,4'-diallyloxydiphenyl sulfone includes sodium hydroxide and potassium hydroxide, and the alkaline earth metal hydroxide is hydroxide. Magnesium, calcium hydroxide, etc., as carbonates, there are sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., and as halides, 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 heat rearrangement reaction of 4,4′-diallyloxydiphenyl sulfone is carried out without solvent,
Or, in an inert water-insoluble organic solvent such as an aliphatic hydrocarbon solvent having a high boiling point and an aromatic organic solvent,
It can be carried out by heating to 0 ° C. After the completion of the reaction, the reaction mixture is purified by an operation such as alkali extraction, solvent extraction, washing, acid precipitation, and recrystallization to give 3,3'-diallyl-, which has excellent performance as a color developer for heat-sensitive recording materials.
4,4'-dihydroxydiphenyl sulfone can be obtained.

[0009]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In Examples and Comparative Examples, the total amount of contained alkali was determined as follows. That is, 4,4′-diallyloxydiphenyl sulfone 30 g
Was dissolved in 450 g of dimethyl sulfoxide, and 10 mL of a 1/50 mol / L aqueous sodium hydroxide solution was added.
Titration was performed using 1/100 mol / L hydrochloric acid, and the total amount of the contained alkali was converted to a sodium hydroxide content as compared with a value obtained by titration without adding 4,4′-diallyloxydiphenyl sulfone. Example 1 In a four-necked flask, 413 g of 4,4′-diallyloxydiphenyl sulfone having a total alkali content of 5 ppm (weight ratio) calculated as sodium hydroxide, and Diana Fresia W-
8 [Idemitsu Kosan Co., Ltd.] 275 g and kerosene [Daiko Sekiyu KK]
275 g was charged and the mixture was heated at 205-210 ° C.
The heat rearrangement reaction was carried out for hours. HPLC of reaction mixture after reaction
The composition ratio (area percentage) was 3,3′-diallyl-4,4′-
91.3% of dihydroxydiphenyl sulfone (hereinafter abbreviated as di-rearranged product), 5- (3-allyl-4-hydroxy)
Phenylsulfonyl-1-oxa-2-methylindane (hereinafter abbreviated as indane form) 1.8%, 3-allyl-
2.9% of 4-hydroxy-4'-allyloxydiphenylsulfone (hereinafter abbreviated as monotransferred), 3-allyl-4,4'-dihydroxydiphenylsulfone (hereinafter abbreviated as monoallyl) 1.1 %Met. The reaction mixture was cooled and a 13% by weight aqueous sodium hydroxide solution 71
After 5 g was added and the mixture was allowed to stand and separated, a four-necked flask was charged with a lower layer aqueous alkali solution and 39 g of activated carbon, and decolorized at 80 ° C. for 1 hour, and the activated carbon was filtered off. Further, the decolorization treatment liquid was charged into a four-necked flask, and 50% by weight at 60 ° C.
184 g of sulfuric acid was added dropwise to perform acid precipitation, and the precipitated crystals were separated by filtration. Crystals separated by filtration in a four-necked flask and ethane dichloride 78
After 0 g was charged, 9.4 g of isopropanol was added, and the mixture was heated under reflux and cooled to 25 ° C. After filtering the precipitated crystals and washing with 300 g of ethane dichloride,
After drying, 293 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained. The obtained 3,3 '
The HPLC composition ratio (area percentage) of the purified diallyl-4,4′-dihydroxydiphenylsulfone was determined to be 9
6.2% and 0.3% of indane. Example 2 Instead of 4,4′-diallyloxydiphenyl sulfone having a total alkali content of 5 ppm (weight ratio) used in Example 1, 4,4 ′ having a total alkali content of 15 ppm (weight ratio) was used.
The reaction was carried out in the same manner as in Example 1 except that 4′-diallyloxydiphenyl sulfone was used. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was 9
The content was 1.0%, the indane form 1.9%, the mono rearrangement form 3.2%, and the monoallyl form 0.9%. Further, by treating in the same manner as in Example 1, 289 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained.
HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product
Was 96.1% of di-isomer and 0.4% of indane.

Example 3 Instead of 4,4'-diallyloxydiphenyl sulfone having a total alkali content of 5 ppm (weight ratio) used in Example 1, 4,3 'having a total alkali content of 30 ppm (weight ratio) was used.
The reaction was carried out in the same manner as in Example 1 except that 4′-diallyloxydiphenyl sulfone was used. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was 9
0.7%, 2.4% of the indane form, 3.0% of the mono rearranged form, and 1.0% of the monoallyl form. Further, the same treatment as in Example 1 was carried out to obtain 281 g of a purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product.
HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product
Was 96.0% of a di-dislocation body and 0.4% of an indane body. Example 4 Instead of 4,4′-diallyloxydiphenyl sulfone having a total alkali content of 5 ppm (weight ratio) used in Example 1, 4,4 ′ having a total alkali content of 45 ppm (weight ratio) was used.
The reaction was carried out in the same manner as in Example 1 except that 4′-diallyloxydiphenyl sulfone was used. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was 8
9.8%, indane form 2.9%, mono rearrangement form 2.8% and monoallyl form 0.9%. Further, the same treatment as in Example 1 was performed to obtain 277 g of a purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product.
HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product
Was 95.9% of di-dislocation and 0.5% of indane.

Comparative Example 1 In a four-necked flask, 413 g of 4,4'-diallyloxydiphenyl sulfone having a total alkali content of 60 ppm (weight ratio) in terms of sodium hydroxide, Diana Fresia W
-8 [Idemitsu Kosan Co., Ltd.] 275 g and kerosene [Daiko Sekiyu
Co., Ltd.], 275 g, and under nitrogen stream, 205-210
A heat rearrangement reaction was performed at 7 ° C. for 7 hours. H of the reaction mixture after the reaction
The PLC composition ratio (area percentage) was 87.8% of di-dislocation body,
4.8% of the indane form, 3.2% of the mono rearranged form, and 1.4% of the monoallyl form. The reaction mixture was cooled, 715 g of a 13% by weight aqueous sodium hydroxide solution was added thereto, and the mixture was allowed to stand for separation. Thereafter, a lower layer aqueous alkali solution and 39 g of activated carbon were charged into a four-necked flask, and decolorized at 80 ° C. for 1 hour. Activated carbon was filtered off. The decolorizing solution was charged into a four-necked flask, and 184 g of 50% by weight sulfuric acid was added dropwise at 60 ° C. to perform acid precipitation, and the precipitated crystals were separated by filtration. A four-necked flask was charged with the filtered crystals and 780 g of ethane dichloride, 9.4 g of isopropanol was added thereto, and the mixture was heated to reflux and then cooled to 25 ° C. The precipitated crystals are separated by filtration and ethane dichloride 300
g, and then dried, and purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product 24
8 g were obtained. The HPLC composition ratio (area percentage) of the purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone obtained was 92.2% for the di-transposition form and 1. for the indane form.
6%. Comparative Example 2 Instead of 4,4'-diallyloxydiphenyl sulfone having a total alkali content of 5 ppm (weight ratio) used in Comparative Example 1, 4,100 having a total alkali content of 100 ppm (weight ratio) was used.
The reaction was carried out in the same manner as in Comparative Example 1, except that 4'-diallyloxydiphenyl sulfone was used. The HPLC composition ratio (area percentage) of the reaction mixture after the reaction was 8
6.9%, indan form 6.2%, mono rearrangement 3.1% and monoallyl form 1.5%. Further, by treating in the same manner as in Example 1, 235 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained.
HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product
Was 93.0% of di-dislocation and 1.8% of indane.
Table 1 shows the results of Examples 1 to 4 and Comparative Examples 1 and 2.

[0012]

[Table 1]

As shown in Table 1, in Examples 1 to 4 in which the total amount of alkali contained in 4,4'-diallyloxydiphenyl sulfone is 5 to 45 ppm (weight ratio), the yield of purified products is High rate, 3,3'-diallyl-4,4 '
A high content of dihydroxydiphenylsulfone;
-(3-allyl-4-hydroxy) phenylsulfonyl-
Low content of 1-oxa-2-methylindane and high purity. In addition, the smaller the total alkali content, the higher the purified product yield and purity. On the other hand, 4,4 '
-In Comparative Examples 1 and 2 in which the total amount of alkali contained in diallyloxydiphenyl sulfone is 60 to 100 ppm (weight ratio), both the yield and purity of the purified product are low.

[0014]

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.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Nishikawa 4-231-1, Bunkyo, Fukui City, Fukui Prefecture Within Nichika Chemical Co., Ltd. (72) Inventor Go Yoshino 4-231-1, Bunkyo, Fukui City, Fukui Prefecture Within Nikka Chemical Co., Ltd. (72) Inventor Toshiaki Takahashi 4-23-1, Bunkyo, Fukui City, Fukui Prefecture Nikka Chemical Co., Ltd. F-term (reference) 2H026 AA07 BB30 4H006 AA02 AC42 BC10 BD10 TA02 TB13 TB42 4H039 CA60 CJ10

Claims (1)

[Claims] 1. A method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone by subjecting 4,4'-diallyloxydiphenylsulfone to a heat rearrangement reaction, wherein 4,4'-diallyloxydiphenylsulfone is produced. 3. A process for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone, wherein the total amount of alkali contained therein is reduced to 50 ppm (weight ratio) or less in terms of sodium hydroxide, followed by heat rearrangement reaction. .