JP2002114757A - Method for producing 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone useful as a developer for heat-sensitive recording materials in high yield in a slight production amount of a component causing halation. SOLUTION: This method for producing 3,3'-diallyl-4,4'-dihydroxydi-phenyl sulfone is characterized by adding 0.5-20 equivalent amount of acid to an alkali contained in 4,4'-diallyloxy-diphenyl sulfone and subjecting the above compound to thermal rearrangement reaction in the method for producing 3,3'-diallyl-4,4'- dihydroxydiphenyl sulfone by carrying out thermal rearrangement of 4,4'- diallyloxydiphenyl sulfone.

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-60-169456 discloses that as a novel phenolic compound useful as a color developer in thermal recording, 4,4'-dihydroxydiphenyl sulfone or an alkali metal salt thereof is reacted with allyl halide, A method for producing 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone to be rearranged has been proposed. Also, JP-A-61-89090 and JP-A-62
No. 53957 describes 3,3′- with less background fog.
As a method for producing diallyl-4,4'-dihydroxydiphenylsulfone, 3-allyl-4'-allyloxy-4
-Hydroxydiphenyl sulfone is 5 to 20% by weight of 4,4'-diallyloxydiphenyl sulfone, and 3,3 '
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 rearrangement reaction. The reaction mixture was extracted with an alkaline solution and subjected to acid precipitation, and then purified by recrystallization using a mixed solvent of a dichloroalkane-based solvent, an aromatic-based solvent and an alcohol-based or glycol-based solvent, and purified by 3,3'-diallyl- 4,4'-Dihydroxydiphenyl sulfone is obtained. Further, JP-A-11-29549 discloses DSC (Te) as a developing compound of a heat-sensitive recording material having high sensitivity, little background fogging component when wet and having excellent image stability.
Is 149 ° C. or higher, and at least a diffraction angle (2θ) [゜] 7.2 in a powder X-ray diffraction method using Cu-Kα radiation.
And a crystal form characterized by an X-ray diffraction pattern having peaks at 22.0 and a crystal having a content of 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone of 96% by weight or more. Materials have been proposed. 4,4 '
-Diallyloxydiphenyl sulfone is heated and rearranged in an inert high-boiling water-insoluble organic solvent so that the amount of 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone is 89 to 93% by weight, and the reaction is carried out. After completion, extraction with an alkaline aqueous solution, partial neutralization with hydrochloric acid, purification using activated carbon, and then precipitation in an aqueous acid solution to precipitate crystals, or extraction with an aqueous alkaline solution, followed by extraction with water and water-insoluble An aqueous organic solvent is added, and the mixture is further neutralized with hydrochloric acid to separate an aqueous layer and an oil layer. An aqueous acid solution is added to the aqueous layer to give 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone. Have gained. In the 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone used as a developer of the thermosensitive recording material, 5- (3-
By-products such as allyl-4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane, 3-allyl-4-hydroxy-4′-allyloxydiphenylsulfone, and 3-allyl-4,4′-dihydroxydiphenylsulfone When a lot of things are included, the 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 are difficulties in inexpensive and industrial production. Therefore, there has been a demand for a method for economically producing 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone having a high purity and a low background fog component.

[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 raw material 4,4
Causal relationship between the total amount of alkali contained in 4'-diallyloxydiphenyl sulfone and the amount of 5- (3-allyl-4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane which is a background fog component And reducing the total amount of alkali contained in the raw material 4,4′-diallyloxydiphenylsulfone,
The inventors have found that 3'-diallyl-4,4'-dihydroxydiphenylsulfone can be obtained with a low background fog component and a high yield, and based on this finding, the present invention has been completed. That is, the present invention provides (1) 4,4′-
In a method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone by heat rearrangement of diallyloxydiphenylsulfone, 0.5 to alkali contained in 4,4'-diallyloxydiphenylsulfone is used. A method of producing 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone, which is characterized in that a heat rearrangement reaction is carried out after adding an acid in an amount of up to 20 equivalents, and (2)
For 4,4′-diallyloxydiphenyl sulfone,
0.01 to 1% by weight of an amine compound and / or 0.01 to 1% by weight
3. The 3,3'- according to claim 1, wherein 1% by weight of an antioxidant is added.
A method for producing diallyl-4,4'-dihydroxydiphenylsulfone. Furthermore, as a preferred embodiment of the present invention, (3) the method for producing 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone according to item 1, wherein the acid is sulfuric acid or phosphoric acid, and (4) 3. The method according to claim 2, wherein the antioxidant is a phenolic antioxidant.
A method for producing 3′-diallyl-4,4′-dihydroxydiphenyl sulfone can be mentioned.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method of the present invention, 4,4'-
In the method for producing 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone by heat rearrangement of diallyloxydiphenylsulfone, an alkali contained in 4,4′-diallyloxydiphenylsulfone as a raw material is used. After adding 0.5 to 20 equivalents of the acid, a heat rearrangement reaction is performed. The heat rearrangement reaction of 4,4′-diallyloxydiphenyl sulfone is carried out in a solvent-free state or in an inert water-insoluble organic solvent such as an aliphatic hydrocarbon solvent having a high boiling point or an aromatic hydrocarbon solvent; It can be carried out by heating to ° C. The amount of alkali contained in 4,4′-diallyloxydiphenyl sulfone is 4,4′-diallyloxydiphenyl sulfone.
It can be measured by dissolving 4'-diallyloxydiphenyl sulfone in an organic solvent such as dimethylsulfoxide and dimethylformamide and titrating with an acid. Since the amount of alkali contained in 4,4′-diallyloxydiphenylsulfone as a raw material is very small, 4,4′-diallyloxydiphenylsulfone is dissolved in an organic solvent,
After adding a predetermined amount of alkali such as an aqueous solution of sodium hydroxide, titration with hydrochloric acid or the like, comparing with a blank test, it is preferable to obtain by converting the total amount of alkali contained to the amount of sodium hydroxide. .

[0006] 4,4'-diallyloxydiphenylsulfone is usually prepared by combining 4,4'-dihydroxydiphenylsulfone and allyl halide in an organic solvent such as an alkali metal or alkaline earth metal hydroxide, carbonate or the like. It is produced by performing a dehydrohalogenation reaction in the presence of an alkali. Therefore, alkalis contained in 4,4′-diallyloxydiphenyl sulfone include hydroxides and carbonates of alkali metals or alkaline earth metals.
There are alkali metal salts and alkaline earth metal salts of 4'-dihydroxydiphenyl sulfone, and alkali metal salts and alkaline earth metal salts of 4-allyloxy-4'-hydroxydiphenyl sulfone. The amounts of these alkalis can be titrated with an acid and expressed, for example, as the total amount of alkali converted to the amount of sodium hydroxide. The alkali contained in 4,4'-diallyloxydiphenylsulfone as a raw material of 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone is obtained by the reaction of 4,4'-dihydroxydiphenylsulfone with allyl halide. Before separating the 4,4′-diallyloxydiphenyl sulfone crystals from the reaction mixture obtained, neutralization by adding an acid is performed, or the 4,4′-diallyloxydiphenyl sulfone crystals are purified using pure water. It is possible to reduce the amount by cleaning. However, it is difficult to completely remove the alkali contained in 4,4′-diallyloxydiphenyl sulfone, and the presence of a trace amount of alkali is inevitable.

The alkali contained in 4,4'-diallyloxydiphenylsulfone is removed by washing with water or the like, and the total amount of alkali is reduced to carry out a heat rearrangement reaction. As a result, 5- (3-allyl-4) which is a background fog component is obtained. -Hydroxy) phenylsulfonyl-1-oxa-2-methylindane, as well as by-products such as 3-allyl-4-hydroxy-4'-allyloxydiphenylsulfone and 3-allyl-4,4'-dihydroxydiphenylsulfone Can be suppressed to some extent, but by further adding an acid and reacting, the generation of by-products such as background fog components can be further suppressed. In a state where the total amount of alkalis is large, when a heat rearrangement reaction is performed using 4,4′-diallyloxydiphenyl sulfone as a raw material without adding an acid, formation of a background fog component and the like is promoted, and
By-products are also generated from 3′-diallyl-4,4′-dihydroxydiphenyl sulfone, making purification difficult,
The purity of 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone decreases, the yield decreases due to the removal of background fog components, or causes of background fog when used as a color developer Becomes However, by adding an acid to 4,4′-diallyloxydiphenyl sulfone and performing a heat rearrangement reaction, even when a raw material having a large total amount of alkalis is used, generation of by-products such as background fog components can be suppressed. .

In the method of the present invention, the alkali contained in 4,4'-diallyloxydiphenyl sulfone is 0.5 to 20 equivalent times, preferably 0.9 to 10 equivalent times.
More preferably, 1 to 3 equivalents of the acid is added. 4,4'-
By adding an acid to diallyloxydiphenyl sulfone and then subjecting it to a heat rearrangement reaction, generation of a background fog component can be suppressed, and high-purity 3,3′-diallyl-
4,4'-dihydroxydiphenyl sulfone can be obtained in high yield. The amount of acid added is 0.5
If it is less than the equivalent, 5- (3-allyl-4-hydroxy) phenylsulfonyl-1-oxa- is required during the thermal rearrangement reaction of 4,4′-diallyloxydiphenylsulfone.
Background fog components such as 2-methylindane cannot be suppressed, and the amount of generation may increase. If the amount of the acid exceeds 20 equivalents of the alkali, the amount of by-products of the reaction may increase, and the coloring of the reaction product may be increased. There is no particular limitation on the acid used in the method of the present invention, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, formic acid, acetic acid, butyric acid, oxalic acid, citric acid,
Malic acid, tartaric acid, benzoic acid, benzenesulfonic acid, p
-Organic acids such as toluenesulfonic acid. One of these acids can be used alone, or two or more can be used in combination. Among these, sulfuric acid and phosphoric acid can be particularly preferably used.

In the method of the present invention, it is preferable to carry out a thermal rearrangement reaction of 4,4'-diallyloxydiphenyl sulfone by adding an amine compound and / or an antioxidant. There is no particular limitation on the amine compound used, for example,
N, N-dimethylaniline, N, N-diethylaniline,
Examples thereof include N, N-dimethylaminopyridine, benzotriazole, diethylenetriamine, and N, N-dimethylbenzylamine. One of these amine compounds can be used alone, or two or more thereof can be used in combination. By performing the thermal rearrangement reaction of 4,4′-diallyloxydiphenyl sulfone in the presence of an amine compound, the progress of the main reaction of the amine compound can be promoted, and the generation of by-products can be suppressed. The amount of the amine compound to be added is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.7% by weight, based on 4,4'-diallyloxydiphenyl sulfone. If the amount of the amine compound is less than 0.01% by weight based on 4,4′-diallyloxydiphenyl sulfone, the effect of suppressing the generation of by-products may not be sufficiently exhibited. If the amount of the amine compound exceeds 1% by weight based on 4,4′-diallyloxydiphenyl sulfone, an excess of the amine compound coordinates to the phenolic hydroxyl group generated by the rearrangement reaction, or forms a complex or a salt. On the contrary, there is a possibility that the side reaction is promoted and the background fog component is increased.

The antioxidant used in the method of the present invention is not particularly limited. For example, hydroquinone monomethyl ether, hydroquinone monoethyl ether, 3,5-di-tert-butyl-4-hydroxytoluene, 2,2'-methylenebis
(6-t-butyl-3-methylphenol), 1,1,3-
Phenolic antioxidants such as tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane;
Sulfur-based antioxidants such as didodecyl 3'-thiodipropionate, ditetradecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, triphenyl phosphite, diphenyl phosphite Examples thereof include phosphorus-based antioxidants such as decyl and tris (nonylphenyl) phosphite. One of these antioxidants can be used alone, or two or more thereof can be used in combination. Among these antioxidants, phenolic antioxidants can be particularly preferably used. By performing the thermal rearrangement reaction of 4,4′-diallyloxydiphenyl sulfone in the presence of an antioxidant,
Coloring accompanying the progress of the reaction can be suppressed. The addition amount of the antioxidant is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.7% by weight, based on 4,4′-diallyloxydiphenyl sulfone.
If the amount of the antioxidant is less than 0.01% by weight based on 4,4′-diallyloxydiphenyl sulfone, the effect of suppressing coloring may not be sufficiently exhibited.
When the amount of the antioxidant exceeds 1% by weight based on 4,4′-diallyloxydiphenyl sulfone, there is a possibility that by-products of the reaction may increase. According to the method of the present invention, 4,4 ′
After the heat rearrangement reaction of diallyloxydiphenyl sulfone, the reaction mixture is extracted with alkali, and further purified by solvent extraction, washing, acid precipitation, recrystallization, activated carbon purification, etc. High-purity 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone having excellent performance as a coloring agent can be obtained.

[0011]

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 alkali contained in 4,4′-diallyloxydiphenyl sulfone (ppm, weight ratio) was determined by dissolving 30.0 g of 4,4′-diallyloxydiphenyl sulfone in 450 g of dimethyl sulfoxide. Then, after adding 10 mL of a 1/50 mol / L sodium hydroxide aqueous solution, titration was performed using 1/100 mol / L hydrochloric acid, and the total alkali content was converted to sodium hydroxide by comparing with a blank test. I asked. Example 1 In a four-necked flask, 413 g of 4,4′-diallyloxydiphenyl sulfone having a total alkali content of 50 ppm (weight ratio) calculated as sodium hydroxide, a paraffin-based solvent [Idemitsu Kosan Co., Ltd., Diana Fresia W- 8] 275 g,
Kerosene (Daiko Sekiyu KK) 275 g and concentrated sulfuric acid 0.025 g
Was charged. The amount of sulfuric acid added is 1.0 equivalent times the total amount of alkali. A heat rearrangement reaction was carried out at 205 to 210 ° C. for 7 hours under a nitrogen stream. HP of reaction mixture after heat rearrangement reaction
LC composition ratio (area percentage) was 3,3′-diallyl-4,
92.4% of 4'-dihydroxydiphenylsulfone (hereinafter abbreviated as ditransferred), 5- (3-allyl-4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane (hereinafter abbreviated as indane) ) 1.5%, 3-allyl-4-hydroxy-4'-allyloxydiphenylsulfone (hereinafter abbreviated as monotransferred form) 1.9%, 3-
Allyl-4,4'-dihydroxydiphenyl sulfone (hereinafter abbreviated as monoallyl form) was 0.7%. The reaction mixture was cooled, 715 g of a 13% by weight aqueous sodium hydroxide solution was added thereto, and the mixture was stirred and allowed to stand. After separation, the lower layer aqueous alkali solution was charged into a four-necked flask, and water was further added thereto. The concentration was adjusted to 30% by weight. Activated carbon [Nimura Chemical Industry Co., Ltd., Taiko S] 82.6
g at 40 ° C. for 1 hour and activated carbon treatment.
The activated carbon was filtered off at ℃ and washed with 100 g of water. The treated solution treated with activated carbon was charged into a four-necked flask, and water was added to adjust the solid content to 20% by weight.
After adding 10 g dropwise over 3 hours for acid precipitation, the pH was adjusted to 4.5 and stirred for 1 hour. The precipitated crystals are filtered off, and water 3
After washing with 50 g, it was dried to obtain 343 g of purified 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone. The obtained 3,3'-diallyl-4,4'-
The HPLC composition ratio (area percentage) of the purified dihydroxydiphenylsulfone product was 97.3% of the di-transposition form and 0.2% of the indane form.

Example 2 In a four-necked flask, 413 g of 4,4'-diallyloxydiphenylsulfone having a total alkali content of 50 ppm (weight ratio) in terms of sodium hydroxide, a paraffin-based solvent [Idemitsu Kosan Co., Ltd., Diana Fresia W-8] 275 g,
Kerosene (Daiko Sekiyu KK) 275 g, N, N-dimethylaniline 0.4 g, hydroquinone monomethyl ether 0.4 g
And 0.025 g of concentrated sulfuric acid. The amount of sulfuric acid added
It is 1.0 equivalent times the total amount of alkali. Under nitrogen stream, 20
A heat rearrangement reaction was performed at 5 to 210 ° C. for 7 hours. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.5% for di-isomer, 1.6% for indane, and 1.
9% and the monoallyl derivative were 0.5%. The reaction mixture was cooled and a 13 wt.
g, and the mixture was stirred and separated by standing. The lower layer aqueous alkali solution was charged into a four-necked flask, and water was further added to adjust the solid content concentration to 30% by weight. In this extract,
82.6 g of activated carbon [Nimura Chemical Industry Co., Ltd., Taiko S] was added, activated carbon treatment was performed at 40 ° C. for 1 hour, the activated carbon was filtered off at 40 ° C., and washed with 100 g of water. The treated solution treated with activated carbon was charged into a four-necked flask, water was added to adjust the solid content to 20% by weight, 410 g of 25% by weight sulfuric acid was added dropwise over 3 hours, and acid precipitation was carried out. Was adjusted to 0.5 and stirred for 1 hour. The precipitated crystals were collected by filtration, washed with 350 g of water, dried, and 3,3′-diallyl-
4,4'-Dihydroxydiphenyl sulfone purified product 351
g was obtained. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was 97.8% for the di-transposition form and 0.1% for the indane form.
Met.

Example 3 Using the same reaction mixture after the heat rearrangement reaction as in Example 2,
715 g of a 13% by weight aqueous sodium hydroxide solution was added,
After standing and separating, a lower layer aqueous alkali solution and activated carbon are placed in a four-necked flask [Takeda Pharmaceutical Co., Ltd., Carbofin 6].
39.0 g was charged, treated with activated carbon at 80 ° C. for 1 hour, and the activated carbon was filtered off at 80 ° C. The treated solution treated with activated carbon was charged into a four-necked flask, and 184 g of 50% by weight sulfuric acid was added dropwise at 60 ° C. to carry out acid precipitation, and the precipitated crystals were separated by filtration. Crystals separated by filtration in a four-necked flask and ethane dichloride 78
0 g, add 9.4 g of isopropanol, and add 1 g.
After heating under reflux for an hour, the mixture was cooled to 25 ° C. The precipitated crystals are filtered off and washed with 300 g of ethane dichloride,
After drying, 330 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained. Three obtained
The HPLC composition ratio (area percentage) of the purified 3'-diallyl-4,4'-dihydroxydiphenylsulfone was 97.2% of the di-transposition compound and 0.2% of the indane compound. Example 4 A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.05 g of concentrated sulfuric acid was charged instead of 0.025 g of concentrated sulfuric acid. The amount of sulfuric acid added is 2.0 equivalent times of the total amount of alkali. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 93.2% for the di-isomer and 1. for the indane.
The content was 2%, the mono-isomer was 2.1%, and the mono-allyl form was 0.5%. Further, by performing the same processing as in the second embodiment,
351 g of purified 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the resulting purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 97.5 in the di-translocation form.
% And the indane body was 0.1%.

Example 5 The total amount of alkali contained in terms of sodium hydroxide was 50 pp
Instead of 413 g of 4,4′-diallyloxydiphenylsulfone m (weight ratio), 413 g of 4,4′-diallyloxydiphenylsulfone having a total alkali content of 100 ppm (weight ratio) in terms of sodium hydroxide was used, A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.10 g of concentrated sulfuric acid was charged instead of 0.025 g of concentrated sulfuric acid. The amount of sulfuric acid added is 2.0 equivalent times of the total amount of alkali. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 93.0% for the di-isomer and 1.4 for the indane.
%, 2.0% of the mono rearranged product, and 0.7% of the monoallyl compound. Further, by performing the same processing as in the second embodiment,
351 g of purified 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 97.4 of the di-transposition product.
%, Indane body was 0.2%. Example 6 Total amount of alkali contained in terms of sodium hydroxide was 50 pp
m (weight ratio) of 413 g of 4,4′-diallyloxydiphenyl sulfone instead of 413 g of 4,4′-diallyloxydiphenyl sulfone having a total alkali content of 20 ppm (weight ratio) in terms of sodium hydroxide, A heat rearrangement reaction was carried out in the same manner as in Example 2, except that 0.01 g of concentrated sulfuric acid was charged instead of 0.025 g of concentrated sulfuric acid. The amount of sulfuric acid added is 1.0 equivalent times the total amount of alkali. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 93.2% for the di-isomer and 1.0 for the indane.
%, The mono-dislocation form was 1.9%, and the mono-allyl form was 0.6%. Further, by performing the same processing as in the second embodiment,
359 g of purified 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 97.7 in the di-transposition form.
% And the indane body was 0.1%.

Example 7 Instead of 0.4 g of N, N-dimethylaniline and 0.4 g of hydroquinone monomethyl ether, 0.2 g of N, N-dimethylaniline and 0.2 g of hydroquinone monomethyl ether
, And a heat rearrangement reaction was carried out in the same manner as in Example 2. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.5% for the di-isomer, 1.6% for the indane, 2.0% for the mono-isomer, and 0.7% for the monoallyl-isomer.
Met. Further, by treating in the same manner as in Example 2, 347 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was 97.
3% and indan form 0.2%. Example 8 Instead of 0.4 g of N, N-dimethylaniline and 0.4 g of hydroquinone monomethyl ether, 2.8 g of N, N-dimethylaniline and 2.8 g of hydroquinone monomethyl ether
, And a heat rearrangement reaction was carried out in the same manner as in Example 2. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.3% for the di-isomer, 1.7% for the indane, 1.9% for the mono-isomer, and 0.5% for the monoallyl-form.
Met. Further, by treating in the same manner as in Example 2, 343 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was 97.
2% and indan form 0.3%.

EXAMPLE 9 Instead of 0.4 g of N, N-dimethylaniline, N, N-dimethylaniline was used.
A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.4 g of dimethylbenzylamine was charged. HPLC composition ratio (area percentage) of reaction mixture after heat rearrangement reaction
Was 92.5% of di-dislocation, 1.6% of indane, 1.9% of mono-dislocation, and 0.6% of mono-allyl. Furthermore, by treating in the same manner as in Example 2, 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product 34
7 g were obtained. The obtained 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product had an HPLC composition ratio (area percentage) of 97.3% for the di-transferred form and 0.1% for the indane form.
2%. Example 10 Instead of 0.4 g of N, N-dimethylaniline used in Example 2, 0.4 of N, N-dimethyl-4-aminopyridine was used.
A heat rearrangement reaction was carried out in the same manner as in Example 2 except that g was charged. HPLC of reaction mixture after heat rearrangement reaction
The composition ratio (area percentage) was 92.4% for di-dislocation, 1.7% for indane, 2.1% for mono-dislocation, and 0.7 for monoallyl.
%Met. Further, by treating in the same manner as in Example 2, 343 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained. The obtained 3,3'-
The HPLC composition ratio (area percentage) of the diallyl-4,4′-dihydroxydiphenylsulfone purified product was determined to be 9
It was 7.3% and the indane body was 0.2%.

Example 11 Instead of 0.4 g of hydroquinone monomethyl ether,
A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.4 g of di-t-butylhydroxytoluene was charged. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.5% for the di-isomer and 1.6 for the indane.
%, 2.0% of the mono rearrangement and 0.6% of the monoallyl compound. Further, by performing the same processing as in the second embodiment,
351 g of purified 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 97.4 of the di-transposition product.
%, Indane body was 0.2%. Example 12 Instead of 0.4 g of hydroquinone monomethyl ether,
A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.4 g of 2,2'-methylenebis- (6-t-butyl-3-methylphenol) was charged. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.5% for the di-isomer, 1.6% for the indane, 2.1% for the mono-isomer,
The monoallyl form was 0.6%. Furthermore, by treating in the same manner as in Example 2, 3,3′-diallyl-4,4′-
347 g of purified dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was 97.4% of the di-transposition form and 0.2% of the indane form.

EXAMPLE 13 Instead of 0.025 g of concentrated sulfuric acid, 85% by weight of phosphoric acid 0.0
A heating rearrangement reaction was carried out in the same manner as in Example 2 except that 5 g was charged. The amount of phosphoric acid added is 2.5 equivalent times of the total amount of alkali. H of the reaction mixture after the heat rearrangement reaction
PLC composition ratio (area percentage) is 92.5% of di-dislocation body,
1.7% of the indane form, 1.4% of the mono rearranged form and 0.7% of the monoallyl form. Further, by treating in the same manner as in Example 2, 343 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 97.3% of the di-transposition form and 0.3% of the indane form. Example 14 Instead of 0.025 g of concentrated sulfuric acid, 85% by weight of phosphoric acid 0.2
A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 5 g was charged. The amount of phosphoric acid added is 1
2.6 equivalent times. H of the reaction mixture after the heat rearrangement reaction
The PLC composition ratio (area percentage) was 92.8% of di-dislocation body,
1.5% of the indane form, 2.4% of the mono rearranged form and 0.4% of the monoallyl form. Further, the same treatment as in Example 2 was performed to obtain 351 g of a purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 97.4% of the di-transposition form and 0.3% of the indane form.

Example 15 A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.05 g of phosphorous acid was charged instead of 0.025 g of concentrated sulfuric acid. The amount of phosphorous acid added is 2.4 equivalent times of the total amount of alkali. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.4% for the di-isomer, 1.7% for the indane, 2.1% for the mono-isomer, and 0.6% for the monoallyl-isomer.
Met. Further, by treating in the same manner as in Example 2, 343 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was 97.
3% and 0.3% of indane. Example 16 A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.25 g of phosphorous acid was charged instead of 0.025 g of concentrated sulfuric acid. The amount of phosphorous acid added was 11.8 of the total amount of alkali.
Equivalent times. HPLC of reaction mixture after heat rearrangement reaction
The composition ratio (area percentage) was 92.6% for di-dislocation, 1.6% for indane, 1.8% for mono-dislocation, and 0.4 for monoallyl.
%Met. Further, by treating in the same manner as in Example 2, 347 g of purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was obtained. The obtained 3,3'-
The HPLC composition ratio (area percentage) of the diallyl-4,4′-dihydroxydiphenylsulfone purified product was determined to be 9
7.4% and 0.2% indane.

Example 17 A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.082 g of concentrated hydrochloric acid was used instead of 0.025 g of concentrated sulfuric acid. The amount of hydrochloric acid added is 1.6 equivalent times of the total amount of alkali. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.2% for the di-isomer and 1. for the indane.
The content was 8%, the mono-isomer was 2.1%, and the mono-allyl form was 0.5%. Further, by performing the same processing as in the second embodiment,
339 g of purified 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was determined to be 97.2 of the di-transposition product.
% And the indane body was 0.3%. Example 18 A heating rearrangement reaction was carried out in the same manner as in Example 2 except that 0.05 g of acetic acid was charged instead of 0.025 g of concentrated sulfuric acid. The amount of acetic acid added is 1.6 equivalent times the total amount of alkali. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.2% for the di rearrangement and 1.8 for the indane.
%, 2.2% of mono-translocation compound and 0.7% of mono-allyl compound. Further, by performing the same processing as in the second embodiment,
339 g of purified 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was determined to be 97.2 of the di-transposition product.
% And the indane body was 0.3%.

Comparative Example 1 Example 2 was repeated except that 0.025 g of concentrated sulfuric acid was not charged.
A heat rearrangement reaction was performed in the same manner as described above. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 90.1% for di-isomer, 3.6% for indane, and 2.2 for mono-rearrangement.
% And the monoallyl compound were 1.0%. Example 2
3,3′-diallyl-4,
322 g of 4'-dihydroxydiphenyl sulfone purified product
I got The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 95.8% of the di-transposition form and 0.5% of the indane form. Comparative Example 2 Using the same reaction mixture after the heat rearrangement reaction as in Comparative Example 1,
By treating in the same manner as in Example 3, 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone purified product 2
81 g were obtained. The HPLC composition ratio (area percentage) of the purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 95.1% for the di-transposition form and 0.1 for the indane form.
5%.

Comparative Example 3 The total amount of alkali contained in terms of sodium hydroxide was 50 pp
Instead of 413 g of 4,4′-diallyloxydiphenylsulfone m (weight ratio), 413 g of 4,4′-diallyloxydiphenylsulfone having a total alkali content of 100 ppm (weight ratio) in terms of sodium hydroxide was used, A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 0.025 g of concentrated sulfuric acid was not charged. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 86.9% for the di-isomer, 7.5% for the indane-isomer, and 2.2 for the mono-isomer.
% And the monoallyl compound was 1.4%. Example 2
3,3′-diallyl-4,
318 g of 4'-dihydroxydiphenyl sulfone purified product
I got The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was 92.9% of the di-transposition form and 2.0% of the indane form. Comparative Example 4 Total alkali content in terms of sodium hydroxide was 50 pp
Instead of 413 g of 4,4′-diallyloxydiphenylsulfone in m (weight ratio), the crystals were washed with water to make the total alkali content in terms of sodium hydroxide 5 ppm (weight ratio). A heat rearrangement reaction was carried out in the same manner as in Example 2 except that 413 g of oxydiphenylsulfone was used and 0.025 g of concentrated sulfuric acid was not charged. The HPLC composition ratio (area percentage) of the reaction mixture after the heat rearrangement reaction was 92.3% for the di rearrangement and 1.8 for the indane.
%, 1.8% of mono rearrangement and 0.8% of mono allyl. Further, by performing the same processing as in the second embodiment,
330 g of purified 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone was obtained. The HPLC composition ratio (area percentage) of the obtained purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone product was determined to be 97.1 of the di-transposition product.
% And the indane body was 0.3%. The types and amounts of the acids, amines and antioxidants of Examples 1 to 18 and Comparative Examples 1 to 4 are shown in Table 1, and the composition of the heat rearrangement reactant, the yield of the purified product and the composition of the purified product are shown in Table 2. . However, the composition is an HPLC composition ratio (area percentage).

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

In Examples 1 to 12 in which sulfuric acid was added to 4,4'-diallyloxydiphenylsulfone as the starting material, 5- (3-allyl-4-) was compared with Comparative Examples 1 to 3 in which no acid was added to the starting material. The amount of (hydroxy) phenylsulfonyl-1-oxa-2-methylindane produced is reduced, and the purity and yield of the purified 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone are improved. Compared to Comparative Example 4 in which the raw material 4,4'-diallyloxydiphenyl sulfone was washed with water to reduce the total amount of alkali, the same or more effect was exhibited by a simple operation of adding sulfuric acid.
Examples 13 to 14 in which phosphoric acid was added to the raw materials, Examples 15 to 16 in which phosphorous acid was added, and Example 17 in which hydrochloric acid was added.
And Comparative Example 1 also in Example 18 in which acetic acid was added.
As compared with 3, the production amount of 5- (3-allyl-4-hydroxy) phenylsulfonyl-1-oxa-2-methylindane was decreased, and 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone was purified. Product purity and yield are improved.

[0028]

According to the method of the present invention, a simple operation of adding an acid to the raw material 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone makes it suitable as a developer for a thermosensitive recording material. A high-purity 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone which can be used and has little background fog can be produced in high yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Nishikawa 4-231-1, Bunkyo, Fukui City, Fukui Prefecture Inside Nikka Kagaku Co., Ltd. (72) Toshiaki Takahashi 4-231-1, Bunkyo, Fukui City, Fukui Prefecture F-term in Nichika Chemical Co., Ltd. (reference) 2H026 AA07 BB30 4H006 AA02 AC27 BA50 BA51 BA66 BD10 BE03 BE04 4H039 CA60 CJ10

Claims (2)

[Claims] 1. A process for producing 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone by heat rearranging 4,4'-diallyloxydiphenyl sulfone.
3,3'-diallyl-4,4 'characterized by adding 0.5 to 20 equivalents of acid to the alkali contained in 4,4'-diallyloxydiphenylsulfone and then subjecting it to heat rearrangement reaction. -A method for producing dihydroxydiphenyl sulfone. 2. An amount of 0.01 to 1% by weight of an amine compound and / or 4,4'-diallyloxydiphenyl sulfone.
The method for producing 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone according to claim 1, wherein 0.01 to 1% by weight of an antioxidant is added.