JPH06107623A - Production of high-purity 2,4-'-dihydroxy-diphenyl sulfones - Google Patents
Production of high-purity 2,4-'-dihydroxy-diphenyl sulfonesInfo
- Publication number
- JPH06107623A JPH06107623A JP5152921A JP15292193A JPH06107623A JP H06107623 A JPH06107623 A JP H06107623A JP 5152921 A JP5152921 A JP 5152921A JP 15292193 A JP15292193 A JP 15292193A JP H06107623 A JPH06107623 A JP H06107623A
- Authority
- JP
- Japan
- Prior art keywords
- purity
- weight
- dihydroxydiphenylsulfones
- mixed solvent
- dihydroxydiphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高純度２,４'−ジヒドロ
キシジフェニルスルホン類の製造方法に関するものであ
る。さらに詳しくいえば、フェノール類と硫酸とから得
られた粗製の２,４'−ジヒドロキシジフェニルスルホン
類を精製して、感熱紙用顕色剤などとして有用な高純度
の２,４'−ジヒドロキシジフェニルスルホン類を効率よ
く製造する方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing high-purity 2,4'-dihydroxydiphenyl sulfones. More specifically, crude 2,4'-dihydroxydiphenyl sulfone obtained from phenols and sulfuric acid is purified to obtain highly pure 2,4'-dihydroxydiphenyl useful as a developer for thermal paper. The present invention relates to a method for efficiently producing sulfones.
【０００２】[0002]
【従来の技術】近年、感熱紙用顕色剤として様々なフェ
ノール系化合物が開発されているが、その中でも２,４'
−ジヒドロキシジフェニルスルホン類は極めて有用な感
熱紙用顕色剤として期待されている。しかしながら、
２,４'−ジヒドロキシジフェニルスルホン類をフェノー
ル類と硫酸との反応により製造した場合、感熱紙用顕色
剤などとして使用可能な高純度のものは得られない。例
えば、フェノール類と硫酸との反応により、２,４'−ジ
ヒドロキシジフェニルスルホンを製造する場合、最適反
応条件を用いても、２,４'−ジヒドロキシジフェニルス
ルホンと４,４'−ジヒドロキシジフェニルスルホンとの
生成比率が重量比で約５０：５０の異性体混合物しか得
られない。また、フェノールとｐ−クレゾールを用いて
５−メチル−２,４'−ジヒドロキシジフェニルスルホン
を製造する場合、あるいはフェノールと２,４−キシレ
ノールを用いて３,５−ジメチル−２,４'−ジヒドロキ
シジフェニルスルホンを製造する場合、２,４'−ジヒド
ロキシ体の生成比率は８０〜９０重量％程度である。従
来、４,４'−ジヒドロキシジフェニルスルホン類の精製
法については様々な試みがなされ、異性体の２,４'−ジ
ヒドロキシジフェニルスルホン類を除去する努力が払わ
れてきたが、２,４'−ジヒドロキシジフェニルスルホン
類の純度を高める精製法については、報告がないのが実
状である。2. Description of the Related Art In recent years, various phenol compounds have been developed as a developer for thermal paper. Among them, 2,4 '
-Dihydroxydiphenyl sulfones are expected as extremely useful developers for thermal paper. However,
When 2,4'-dihydroxydiphenyl sulfones are produced by the reaction of phenols and sulfuric acid, a highly pure product usable as a developer for thermal paper cannot be obtained. For example, when 2,4′-dihydroxydiphenylsulfone is produced by the reaction of phenols and sulfuric acid, 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone are produced even if the optimum reaction conditions are used. Only a mixture of isomers having a production ratio of about 50:50 by weight can be obtained. Further, when 5-methyl-2,4'-dihydroxydiphenyl sulfone is produced using phenol and p-cresol, or 3,5-dimethyl-2,4'-dihydroxy is produced using phenol and 2,4-xylenol. When diphenyl sulfone is produced, the production ratio of 2,4′-dihydroxy compound is about 80 to 90% by weight. Conventionally, various attempts have been made to purify 4,4′-dihydroxydiphenylsulfones, and efforts have been made to remove the isomer 2,4′-dihydroxydiphenylsulfones. The fact is that there is no report on a purification method for increasing the purity of dihydroxydiphenyl sulfones.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、フェノール類と硫酸とから得られる粗製
の２,４'−ジヒドロキシジフェニルスルホン類を精製し
て、感熱紙用顕色剤などとして有用な高純度２,４'−ジ
ヒドロキシジフェニルスルホン類を効率よく製造する方
法を提供することを目的としてなされたものである。Under the circumstances described above, the present invention purifies crude 2,4'-dihydroxydiphenylsulfones obtained from phenols and sulfuric acid to obtain a paper for thermal paper. The object of the present invention is to provide a method for efficiently producing high-purity 2,4′-dihydroxydiphenyl sulfones useful as a colorant or the like.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、精製溶媒とし
て特定の溶媒を用いることにより、その目的を達成しう
ることを見い出し、この知見に基づいて本発明を完成す
るに至った。すなわち、本発明は、フェノール類と硫酸
との反応により得られた粗製の２,４'−ジヒドロキシジ
フェニルスルホン類を精製して、高純度の２,４'−ジヒ
ドロキシジフェニルスルホン類を製造するに当たり、精
製溶媒として、（１）低級脂肪族アルコール類の中から
選ばれた少なくとも１種５〜２０重量％と非ハロゲン系
芳香族炭化水素の中から選ばれた少なくとも１種９５〜
８０重量％とから成る混合溶媒、（２）ケトン類の中か
ら選ばれた少なくとも１種１０〜４０重量％と非ハロゲ
ン系芳香族炭化水素類の中から選ばれた少なくとも１種
９０〜６０重量％とから成る混合溶媒、又は（３）酢酸
エステル類の中から選ばれた少なくとも１種１０〜４０
重量％と非ハロゲン系芳香族炭化水素類の中から選ばれ
た少なくとも１種９０〜６０重量％とから成る混合溶媒
を用い、処理することを特徴とする高純度２,４'−ジヒ
ドロキシジフェニルスルホン類の製造方法を提供するも
のである。Means for Solving the Problems The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, found that the object can be achieved by using a specific solvent as a purification solvent. The present invention has been completed based on this finding. That is, the present invention purifies crude 2,4′-dihydroxydiphenylsulfones obtained by the reaction of phenols and sulfuric acid to produce high-purity 2,4′-dihydroxydiphenylsulfones, As a refining solvent, (1) 5 to 20% by weight of at least one selected from lower aliphatic alcohols and at least one selected from 95 to 95% of non-halogenated aromatic hydrocarbons
80% by weight of mixed solvent, (2) 10 to 40% by weight of at least one selected from ketones and 90 to 60% by weight of at least one selected from non-halogenated aromatic hydrocarbons % And at least one selected from the group consisting of (3) acetic acid esters 10 to 40
High-purity 2,4′-dihydroxydiphenyl sulfone, which is treated by using a mixed solvent consisting of 90% by weight and 90% by weight of at least one selected from non-halogenated aromatic hydrocarbons. The present invention provides a method for manufacturing a class of products.
【０００５】以下、本発明を詳細に説明する。本発明に
おいては、フェノール類と硫酸とから得られた粗製の
２,４'−ジヒドロキシジフェニルスルホン類を特定の溶
媒を用いて精製し、高純度の２,４'−ジヒドロキシジフ
ェニルスルホン類を製造する。原料のフェノール類とし
ては、例えばフェノール、ｏ−クレゾール、ｍ−クレゾ
ール、２,３−キシレノール、２,５−キシレノール、
３,５−キシレノールなどの少なくとも１つのオルソ位
及びパラ位が共に無置換のフェノール類の中から選ばれ
た１種又は２種の混合物、あるいはこれらのフェノール
類の中から選ばれた１種とｐ−クレゾール、２,４−キ
シレノール、２,６−キシレノール、３,４−キシレノー
ルなどの２つのオルソ位又はパラ位が置換されているフ
ェノール類の中から選ばれた１種との混合物を挙げるこ
とができる。これらのフェノール類と硫酸との使用割合
については、モル比が２：１ないし４：１の範囲にある
ように用いるのが好ましい。該フェノール類と硫酸との
反応は、通常１００〜２００℃の範囲の温度に加熱し、
反応生成水を系外へ留去させながら行われる。反応生成
水の系外への留去方法については特に制限はなく、減圧
にして留去させてもよいし、窒素ガスなどの不活性ガス
を反応系に導入することにより留去させてもよく、ある
いは適当な溶媒を用いて、共沸により留去させてもよ
い。また、該反応には、所望により触媒を用いることが
できる。この触媒としては、例えばホスホン酸、ホスフ
ィン酸、リン酸及びそれらの塩などが挙げられる。これ
らの触媒の使用量は、通常硫酸に対して２重量％以上、
好ましくは５〜１０重量％の範囲で選ばれる。The present invention will be described in detail below. In the present invention, crude 2,4′-dihydroxydiphenyl sulfones obtained from phenols and sulfuric acid are purified using a specific solvent to produce highly pure 2,4′-dihydroxydiphenyl sulfones. . Examples of the raw material phenols include phenol, o-cresol, m-cresol, 2,3-xylenol, 2,5-xylenol,
At least one ortho-position and para-position such as 3,5-xylenol selected from the group consisting of unsubstituted phenols or a mixture of two kinds, or one selected from these phenols. P-Cresol, 2,4-xylenol, 2,6-xylenol, and a mixture with one kind selected from phenols substituted at two ortho or para positions such as 3,4-xylenol are mentioned. be able to. With respect to the usage ratio of these phenols and sulfuric acid, it is preferable to use them so that the molar ratio is in the range of 2: 1 to 4: 1. The reaction between the phenols and sulfuric acid is usually carried out by heating to a temperature in the range of 100 to 200 ° C,
It is carried out while distilling off the water produced by the reaction out of the system. The method of distilling the reaction product water out of the system is not particularly limited, and may be distilled under reduced pressure, or may be distilled by introducing an inert gas such as nitrogen gas into the reaction system. Alternatively, it may be removed by azeotropic distillation using a suitable solvent. Further, a catalyst can be used in the reaction, if desired. Examples of this catalyst include phosphonic acid, phosphinic acid, phosphoric acid and salts thereof. The amount of these catalysts used is usually 2% by weight or more with respect to sulfuric acid,
It is preferably selected in the range of 5 to 10% by weight.
【０００６】本発明においては、このようにして得られ
た粗製の２,４'−ジヒドロキシジフェニルスルホン類
を、精製溶媒として、（１）低級脂肪族アルコール類の
中から選ばれた少なくとも１種５〜２０重量％と非ハロ
ゲン系芳香族炭化水素類の中から選ばれた少なくとも１
種９５〜８０重量％とから成る混合溶媒、（２）ケトン
類の中から選ばれた少なくとも１種１０〜４０重量％と
非ハロゲン系芳香族炭化水素類の中から選ばれた少なく
とも１種９０〜６０重量％とから成る混合溶媒、又は
（３）酢酸エステル類の中から選ばれた少なくとも１種
１０〜４０重量％と非ハロゲン系芳香族炭化水素類の中
から選ばれた少なくとも１種９０〜６０重量％とから成
る混合溶媒を用いて処理する。前記（１）の混合溶媒に
おける低級脂肪族アルコール類としては、例えばメタノ
ール、エタノール、ｎ−プロパノール、イソプロパノー
ル、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノ
ール、ｔ−ブタノールなどが挙げられ、これらはそれぞ
れ単独で用いてもよいし、２種以上を混合して用いても
よい。また、非ハロゲン系芳香族炭化水素類としては、
例えばベンゼン、トルエン、キシレン、エチルベンゼ
ン、ブチルベンゼン、ジエチルベンゼン、メシチレン、
シメン、キュメン、プソイドキュメンなどが挙げられ、
これらはそれぞれ単独で用いてもよいし、２種以上を混
合して用いてもよい。該低級脂肪族アルコール類と非ハ
ロゲン系芳香族炭化水素類との割合が前記範囲を逸脱す
ると、本発明の目的が十分達せられない。また、前記
（２）の混合溶媒におけるケトン類としては、例えばア
セトン、メチルエチルケトン、メチルイソブチルケト
ン、２−ペンタノン、３−ペンタノン、２−ヘプタノ
ン、４−ヘプタノン、ジイソブチルケトン、シクロヘキ
サノンなどが挙げられ、これらはそれぞれ単独で用いて
もよいし、２種以上を混合して用いてもよい。一方、非
ハロゲン系芳香族炭化水素類としては、前記（１）の混
合溶媒における非ハロゲン系芳香族炭化水素類の説明に
おいて例示したものと同じものを挙げることができる。
この非ハロゲン系芳香族炭化水素類は１種用いてもよい
し２種以上を組み合わせて用いてもよい。該ケトン類と
非ハロゲン系芳香族炭化水素類との割合が前記範囲を逸
脱すると、本発明の目的が十分に達せられない。In the present invention, the crude 2,4'-dihydroxydiphenyl sulfone thus obtained is used as a refining solvent for at least one of 5 selected from (1) lower aliphatic alcohols. -20% by weight and at least 1 selected from non-halogenated aromatic hydrocarbons
95 to 80% by weight of mixed solvent, 10 to 40% by weight of at least one selected from (2) ketones and at least one selected from non-halogenated aromatic hydrocarbons 90 Mixed solvent consisting of ˜60% by weight, or at least one kind selected from (3) acetic acid esters 10 to 40% by weight and at least one kind selected from non-halogenated aromatic hydrocarbons 90 Treatment with a mixed solvent consisting of ˜60% by weight. Examples of the lower aliphatic alcohol in the mixed solvent (1) include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, etc. May be used, or two or more kinds may be mixed and used. Further, as non-halogenated aromatic hydrocarbons,
For example, benzene, toluene, xylene, ethylbenzene, butylbenzene, diethylbenzene, mesitylene,
Simmen, cumene, pseudocumene, etc.
These may be used alone or in combination of two or more. If the ratio of the lower aliphatic alcohols to the non-halogenated aromatic hydrocarbons deviates from the above range, the object of the present invention will not be sufficiently achieved. Examples of the ketones in the mixed solvent (2) include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, and the like. May be used alone or in combination of two or more. On the other hand, as the non-halogenated aromatic hydrocarbons, the same ones as exemplified in the description of the non-halogenated aromatic hydrocarbons in the mixed solvent of the above (1) can be mentioned.
These non-halogenated aromatic hydrocarbons may be used alone or in combination of two or more. If the ratio of the ketones and the non-halogenated aromatic hydrocarbons deviates from the above range, the object of the present invention cannot be fully achieved.
【０００７】さらに、前記（３）の混合溶媒における酢
酸エステルとしては、例えば酢酸メチル、酢酸エチル、
酢酸プロピル、酢酸ブチルなどが挙げられ、これらはそ
れぞれ単独で用いてもよいし、２種以上を混合して用い
てもよい。一方、非ハロゲン系芳香族炭化水素類として
は、前記（１）の混合溶媒における非ハロゲン系芳香族
炭化水素類の説明において例示したものと同じものを挙
げることができる。この非ハロゲン系芳香族炭化水素類
は１種用いてもよいし、２種以上を組み合わせて用いて
もよい。該酢酸エステル類と非ハロゲン系芳香族炭化水
素類との割合が前記範囲を逸脱すると、本発明の目的が
十分に達せられない。本発明方法においては、フェノー
ル類と硫酸との反応により得られた粗製の２,４'−ジヒ
ドロキシジフェニルスルホン類を、前記混合溶媒に加
え、加熱して溶解させたのち、冷却し、未溶解物の異性
体などを公知の手段、例えばろ過や遠心分離などの方法
により取り出し、次いで残液から低級脂肪族アルコール
類、ケトン類又は酢酸エステル類を留去させることによ
って、所望する高純度の２,４'−ジヒドロキシジフェニ
ルスルホン類が得られる。この際、混合溶媒における各
成分の混合割合及び混合溶媒の使用量は、精製に用いる
粗製の２,４'−ジヒドロキシジフェニルスルホン類の純
度及び処理量によって適宜決められる。また、加熱温度
や冷却温度は使用する混合溶媒の種類などに応じて適宜
選ばれる。本発明方法によると、精製条件を適当に選択
することにより、純度９５重量％以上の２,４'−ジヒド
ロキシジフェニルスルホン類を製造することも可能であ
る。また、精製溶媒として、環境に悪影響を及ぼすジク
ロロエタンやｏ−ジクロロベンゼンに代表されるハロゲ
ン系炭化水素を使用しないため、環境衛生上及び工業的
に極めて有利に実施しうる。Further, as the acetic acid ester in the mixed solvent of the above (3), for example, methyl acetate, ethyl acetate,
Examples thereof include propyl acetate and butyl acetate, and these may be used alone or in combination of two or more kinds. On the other hand, as the non-halogenated aromatic hydrocarbons, the same ones as exemplified in the description of the non-halogenated aromatic hydrocarbons in the mixed solvent of the above (1) can be mentioned. These non-halogenated aromatic hydrocarbons may be used alone or in combination of two or more. If the ratio of the acetic acid ester and the non-halogenated aromatic hydrocarbon deviates from the above range, the object of the present invention cannot be sufficiently achieved. In the method of the present invention, crude 2,4′-dihydroxydiphenyl sulfone obtained by the reaction of phenols and sulfuric acid is added to the mixed solvent, heated and dissolved, and then cooled to obtain an undissolved substance. The isomers of the above are taken out by a known means, for example, a method such as filtration or centrifugation, and then the lower aliphatic alcohols, ketones or acetic acid esters are distilled off from the residual liquid to obtain a desired high purity 2, 4'-dihydroxydiphenyl sulfones are obtained. At this time, the mixing ratio of each component in the mixed solvent and the amount of the mixed solvent used are appropriately determined depending on the purity and the amount of the crude 2,4′-dihydroxydiphenylsulfones used for purification. Further, the heating temperature and the cooling temperature are appropriately selected depending on the type of mixed solvent used. According to the method of the present invention, it is possible to produce 2,4′-dihydroxydiphenylsulfones having a purity of 95% by weight or more by appropriately selecting the purification conditions. Further, since a halogen-based hydrocarbon represented by dichloroethane or o-dichlorobenzene, which has an adverse effect on the environment, is not used as a purification solvent, it can be carried out extremely advantageously in terms of environmental hygiene and industrially.
【０００８】[0008]
【実施例】次に実施例により本発明をさらに詳細に説明
するが、本発明はこれらの例によってなんら限定される
ものではない。 実施例１ （１）フェノールと硫酸との反応 反応器にフェノール７９３ｇ、硫酸３３４ｇ及びホスホ
ン酸１６.５ｇを仕込み、５６０〜２６０mmHgの減圧
下、１５０〜１６５℃で３時間脱水反応を行い、流出物
２５０ｇを得たところで、フェノール１６５ｇを加え２
６０〜１００mmHgの減圧下、２時間脱水反応を行い、流
出物１８０ｇを得た。さらにフェノール１６５ｇを加え
２６０〜１００mmHgの減圧下、２時間脱水反応を行い流
出物が１４０ｇになったところで反応を終了し、水洗に
よりフェノールスルホン酸を除去したのち乾燥した。ジ
ヒドロキシジフェニルスルホン異性体混合物が８５モル
％の収率で得られた。高速液体クロマトグラフィーで分
析した結果、２,４'−ジヒドロキシジフェニルスルホン
が４９wt％、４,４'−ジヒドロキシジフェニルスルホン
が５０wt％、その他成分が１wt％の組成であった。 （２）精製 前記（１）で得られた異性体混合物１００ｇをキシレン
２０５ｇとイソプロパノール４５ｇとの混合溶媒に分散
し、２時間加熱還流した。次に４０〜３０℃に冷却し結
晶をろ別、乾燥して４,４'−ジヒドロキシジフェニルス
ルホン４２ｇを得た。ろ液からイソプロパノールを留去
し、析出した結晶をろ取乾燥し、２,４'−ジヒドロキシ
ジフェニルスルホン５３ｇを得た。高速液体クロマトグ
ラフィーで測定した結果、純度９７.０wt％の４,４'−
ジヒドロキシジフェニルスルホンと純度８０.５wt％の
２,４'−ジヒドロキシジフェニルスルホンであった。EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 (1) Reaction of Phenol and Sulfuric Acid A reactor was charged with 793 g of phenol, 334 g of sulfuric acid and 16.5 g of phosphonic acid, and dehydration reaction was carried out at 150 to 165 ° C. for 3 hours under a reduced pressure of 560 to 260 mmHg, and an outflow was obtained. When 250g was obtained, 165g of phenol was added and 2
The dehydration reaction was performed for 2 hours under reduced pressure of 60 to 100 mmHg to obtain 180 g of effluent. Further, 165 g of phenol was added and dehydration reaction was carried out for 2 hours under a reduced pressure of 260 to 100 mmHg. When the effluent amounted to 140 g, the reaction was terminated, the phenolsulfonic acid was removed by washing with water, and then dried. A dihydroxydiphenyl sulfone isomer mixture was obtained with a yield of 85 mol%. As a result of analysis by high performance liquid chromatography, the composition was 49 wt% of 2,4′-dihydroxydiphenyl sulfone, 50 wt% of 4,4′-dihydroxydiphenyl sulfone, and 1 wt% of other components. (2) Purification 100 g of the isomer mixture obtained in (1) above was dispersed in a mixed solvent of 205 g of xylene and 45 g of isopropanol, and the mixture was heated under reflux for 2 hours. Next, the mixture was cooled to 40 to 30 ° C., the crystals were filtered off and dried to obtain 42 g of 4,4′-dihydroxydiphenyl sulfone. Isopropanol was distilled off from the filtrate, and the precipitated crystals were collected by filtration and dried to obtain 53 g of 2,4′-dihydroxydiphenyl sulfone. As a result of measurement by high performance liquid chromatography, 4,7'-purity of 97.0 wt%
It was dihydroxydiphenyl sulfone and 2,4'-dihydroxydiphenyl sulfone having a purity of 80.5 wt%.
【０００９】実施例２ （１）フェノールと硫酸との反応 反応器にフェノール７９３ｇ、硫酸３３４ｇ及びホスフ
ィン酸１６.５ｇを仕込み、５６０〜２６０mmHgの減圧
下、１５０〜１６５℃で３時間脱水反応を行い、流出物
２４０ｇを得たところで、フェノール１６５ｇを加え２
６０〜１００mmHgの減圧下、２時間脱水反応を行い、流
出物１７０ｇを得た。さらにフェノール１６５ｇを加え
２６０〜１００mmHgの減圧下２時間脱水反応を行い流出
物が１２５ｇになったところで反応を終了し、水洗によ
りフェノールスルホン酸を除去したのち乾燥した。ジヒ
ドロキシジフェニルスルホン異性体混合物が８２モル％
の収率で得られた。高速液体クロマトグラフィーで分析
した結果、２,４'−ジヒドロキシジフェニルスルホンが
４０wt％、４,４'−ジヒドロキシジフェニルスルホンが
５８wt％、その他成分が２wt％の組成であった。 （２）精製 前記（１）で得られた異性体混合物１００ｇをキシレン
２２０ｇとイソプロパノール３０ｇとの混合溶媒に分散
し、２時間加熱還流した。次に４０〜３０℃に冷却し結
晶をろ別、乾燥して４,４'−ジヒドロキシジフェニルス
ルホン４５ｇを得た。ろ液からイソプロパノールを留去
し、析出した結晶をろ取、乾燥し２,４'−ジヒドロキシ
ジフェニルスルホン５０ｇを得た。高速液体クロマトグ
ラフィーで測定した結果、純度９７.０wt％の４,４'−
ジヒドロキシジフェニルスルホンと純度７５.５wt％の
２,４'−ジヒドロキシジフェニルスルホンであった。Example 2 (1) Reaction of Phenol with Sulfuric Acid A reactor was charged with 793 g of phenol, 334 g of sulfuric acid and 16.5 g of phosphinic acid, and dehydration reaction was carried out at 150-165 ° C. for 3 hours under a reduced pressure of 560-260 mmHg. When effluent 240g was obtained, 165g of phenol was added to
The dehydration reaction was performed for 2 hours under reduced pressure of 60 to 100 mmHg to obtain 170 g of effluent. Further, 165 g of phenol was added, and dehydration reaction was carried out for 2 hours under a reduced pressure of 260 to 100 mmHg. When the amount of effluent reached 125 g, the reaction was terminated, the phenolsulfonic acid was removed by washing with water, and then dried. 82 mol% of dihydroxydiphenyl sulfone isomer mixture
It was obtained with a yield of. As a result of analysis by high performance liquid chromatography, the composition was 40% by weight of 2,4′-dihydroxydiphenylsulfone, 58% by weight of 4,4′-dihydroxydiphenylsulfone, and 2% by weight of other components. (2) Purification 100 g of the isomer mixture obtained in (1) above was dispersed in a mixed solvent of 220 g of xylene and 30 g of isopropanol, and the mixture was heated under reflux for 2 hours. Next, the mixture was cooled to 40 to 30 ° C., the crystals were separated by filtration and dried to obtain 45 g of 4,4′-dihydroxydiphenyl sulfone. Isopropanol was distilled off from the filtrate, and the precipitated crystals were collected by filtration and dried to obtain 50 g of 2,4'-dihydroxydiphenyl sulfone. As a result of measurement by high performance liquid chromatography, 4,7'-purity of 97.0 wt%
It was dihydroxydiphenyl sulfone and 2,4'-dihydroxydiphenyl sulfone having a purity of 75.5 wt%.
【００１０】実施例３ （１）フェノールと硫酸との反応 反応器にフェノール７９３ｇ、硫酸３３４ｇ、メシチレ
ン９５０ミリリットル及びホスホン酸１６.５ｇを仕込
み、還流下６時間脱水反応を行い、次いで室温まで冷却
したのち、ろ過してフェノールスルホン酸を除去後、乾
燥した。ジヒドロキシジフェニルスルホン異性体混合物
が８５モル％の収率で得られた。高速液体クロマトグラ
フィーで分析した結果、２,４'−ジヒドロキシジフェニ
ルスルホンが５１wt％、４,４'−ジヒドロキシジフェニ
ルスルホンが４８wt％、その他成分が１wt％の組成であ
った。 （２）精製 前記（１）で得られた異性体混合物１００ｇをキシレン
１６０ｇとメチルエチルケトン９０ｇとの混合溶媒に分
散し、２時間加熱還流した。次に４０〜３０℃に冷却し
結晶をろ別、乾燥して４,４'−ジヒドロキシジフェニル
スルホン４２ｇを得た。ろ液からメチルエチルケトンを
留去し、析出した結晶をろ取、乾燥したのち、水／メタ
ノールの混合溶媒で再結晶することにより、２,４'−ジ
ヒドロキシジフェニルスルホン４３ｇを得た。高速液体
クロマトグラフィーで測定した結果、純度９７.０wt％
の４,４'−ジヒドロキシジフェニルスルホンと純度９
７.０wt％の２,４'−ジヒドロキシジフェニルスルホン
であった。Example 3 (1) Reaction of Phenol with Sulfuric Acid A reactor was charged with 793 g of phenol, 334 g of sulfuric acid, 950 ml of mesitylene and 16.5 g of phosphonic acid, dehydration reaction was carried out under reflux for 6 hours, and then cooled to room temperature. After that, it was filtered to remove the phenolsulfonic acid and then dried. A dihydroxydiphenyl sulfone isomer mixture was obtained with a yield of 85 mol%. As a result of analysis by high performance liquid chromatography, the composition was 51% by weight of 2,4′-dihydroxydiphenylsulfone, 48% by weight of 4,4′-dihydroxydiphenylsulfone, and 1% by weight of other components. (2) Purification 100 g of the isomer mixture obtained in (1) above was dispersed in a mixed solvent of 160 g of xylene and 90 g of methyl ethyl ketone, and the mixture was heated under reflux for 2 hours. Next, the mixture was cooled to 40 to 30 ° C., the crystals were filtered off and dried to obtain 42 g of 4,4′-dihydroxydiphenyl sulfone. Methyl ethyl ketone was distilled off from the filtrate, the precipitated crystals were collected by filtration, dried and then recrystallized with a mixed solvent of water / methanol to obtain 43 g of 2,4'-dihydroxydiphenyl sulfone. Purity 97.0 wt% as measured by high performance liquid chromatography
4,4'-dihydroxydiphenyl sulfone and purity 9
It was 7.0 wt% of 2,4'-dihydroxydiphenyl sulfone.
【００１１】実施例４ （１）フェノールと硫酸との反応 反応器にフェノール７９３ｇ、硫酸３３４ｇ、Ｓｈｅｌ
ｌｓｏｌ Ａ９５０ミリリットル及びホスホン酸１６.５
ｇを仕込み、還流下６時間脱水反応を行い、次いで室温
まで冷却したのち、ろ過してフェノールスルホン酸を除
去後、乾燥した。ジヒドロキシジフェニルスルホン異性
体混合物が８０モル％の収率で得られた。高速液体クロ
マトグラフィーで分析した結果、２,４'−ジヒドロキシ
ジフェニルスルホンが５２wt％、４,４'−ジヒドロキシ
ジフェニルスルホンが４７wt％、その他成分が１wt％の
組成であった。 （２）精製 前記（１）で得られた異性体混合物１００ｇをメシチレ
ン１５５ｇと酢酸ブチル９５ｇとの混合溶媒に分散し、
２時間加熱還流した。次に４０〜３０℃に冷却し、結晶
をろ別、乾燥して４,４'−ジヒドロキシジフェニルスル
ホン４５ｇを得た。ろ液から酢酸ブチルを留去し、析出
した結晶をろ取、乾燥して２,４'−ジヒドロキシジフェ
ニルスルホン４１ｇを得た。高速液体クロマトグラフィ
ーで測定した結果、純度９６.５wt％の４,４'−ジヒド
ロキシジフェニルスルホンと純度９７.０wt％の２,４'
−ジヒドロキシジフェニルスルホンであった。Example 4 (1) Reaction of Phenol with Sulfuric Acid In a reactor, 793 g of phenol, 334 g of sulfuric acid, and Shel were placed.
lsol A950 ml and phosphonic acid 16.5
After adding g, the mixture was dehydrated under reflux for 6 hours, cooled to room temperature, filtered to remove phenolsulfonic acid, and then dried. A dihydroxydiphenyl sulfone isomer mixture was obtained with a yield of 80 mol%. As a result of analysis by high performance liquid chromatography, the composition was 52% by weight of 2,4'-dihydroxydiphenylsulfone, 47% by weight of 4,4'-dihydroxydiphenylsulfone, and 1% by weight of other components. (2) Purification 100 g of the isomer mixture obtained in (1) above is dispersed in a mixed solvent of 155 g of mesitylene and 95 g of butyl acetate,
The mixture was heated under reflux for 2 hours. Next, it was cooled to 40 to 30 ° C., and the crystals were separated by filtration and dried to obtain 45 g of 4,4′-dihydroxydiphenyl sulfone. Butyl acetate was distilled off from the filtrate, and the precipitated crystals were collected by filtration and dried to obtain 41 g of 2,4′-dihydroxydiphenyl sulfone. As a result of measurement by high performance liquid chromatography, 4,4'-dihydroxydiphenyl sulfone having a purity of 96.5 wt% and 2,4 'having a purity of 97.0 wt% were obtained.
-Dihydroxydiphenyl sulfone.
【００１２】実施例５ （１）フェノールと２,４−キシレノールとの反応 反応器に２,４−キシレノール４１６ｇ、硫酸３３４
ｇ、Ｓｈｅｌｌｓｏｌ ＡＢ２０００ミリリットル及び
ホスホン酸１６.５ｇを仕込み、還流下３時間脱水反応
を行い、次いでフェノール３８４ｇを加えて４時間脱水
反応を行った。室温まで冷却し、析出した結晶をろ取
し、希アルカリ液にて洗浄したのち、水洗によりフェノ
ールスルホン酸を除去し、乾燥した。ジヒドロキシジフ
ェニルスルホン誘導体の異性体混合物が８０モル％の収
率で得られた。高速液体クロマトグラフィーで分析した
結果、３,５−ジメチル−２,４'−ジヒドロキシジフェ
ニルスルホン（ｍｐ．１７６℃）が８７wt％、その他成
分が１３wt％の組成であった。 （２）精製 前記（１）で得られた異性体混合物１００ｇをメシチレ
ン１５０ｇとメチルイソブチルケトン９０ｇとの混合溶
媒に分散し、２時間還流したのち、４０℃以下に冷却
し、ろ過した。ろ液よりメチルイソブチルケトンを留去
することにより、３,５−ジメチル−２,４'−ジヒドロ
キシジフェニルスルホン６７ｇを得た。高速液体クロマ
トグラフィーで測定した結果、純度９７.５wt％であっ
た。 実施例６ 実施例（１）で得られた異性体混合物１００ｇをキシレ
ン１４０ｇと酢酸ブチル１００ｇとの混合溶媒に分散
し、２時間還流したのち、４０℃以下に冷却し、ろ過し
た。ろ液より酢酸ブチルを留去することにより、３,５
−ジメチル−２,４'−ジヒドロキシジフェニルスルホン
６５ｇを得た。高速液体クロマトグラフィーで測定した
結果、純度９７.０wt％であった。Example 5 (1) Reaction of phenol with 2,4-xylenol 416 g of 2,4-xylenol and 334 of sulfuric acid were placed in a reactor.
g, Shellsol AB (2000 ml) and phosphonic acid (16.5 g) were charged, dehydration reaction was performed under reflux for 3 hours, and then 384 g of phenol was added and dehydration reaction was performed for 4 hours. After cooling to room temperature, the precipitated crystals were collected by filtration, washed with a dilute alkaline solution, washed with water to remove phenolsulfonic acid, and dried. An isomer mixture of dihydroxydiphenyl sulfone derivatives was obtained with a yield of 80 mol%. As a result of analysis by high performance liquid chromatography, the composition was 3,5-dimethyl-2,4'-dihydroxydiphenylsulfone (mp.176 ° C) of 87 wt% and the other components of 13 wt%. (2) Purification 100 g of the isomer mixture obtained in (1) above was dispersed in a mixed solvent of 150 g of mesitylene and 90 g of methyl isobutyl ketone, refluxed for 2 hours, cooled to 40 ° C. or lower, and filtered. The methyl isobutyl ketone was distilled off from the filtrate to obtain 67 g of 3,5-dimethyl-2,4'-dihydroxydiphenyl sulfone. As a result of measurement by high performance liquid chromatography, the purity was 97.5 wt%. Example 6 100 g of the isomer mixture obtained in Example (1) was dispersed in a mixed solvent of 140 g of xylene and 100 g of butyl acetate, refluxed for 2 hours, cooled to 40 ° C. or lower, and filtered. By removing butyl acetate from the filtrate, 3.5
-65 g of dimethyl-2,4'-dihydroxydiphenyl sulfone was obtained. As a result of measurement by high performance liquid chromatography, the purity was 97.0 wt%.
【００１３】[0013]
【発明の効果】本発明方法によると、フェノール類と硫
酸とから得られた粗製の２,４'−ジヒドロキシジフェニ
ルスルホン類を特定の溶媒を用いて精製することによ
り、感熱紙顕色剤などとして有用な高純度の２,４'−ジ
ヒドロキシジフェニルスルホン類が効率よく得られる。According to the method of the present invention, crude 2,4'-dihydroxydiphenyl sulfone obtained from phenols and sulfuric acid is purified by using a specific solvent to obtain a thermal paper developer. Useful high-purity 2,4'-dihydroxydiphenyl sulfones can be efficiently obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 315/00 315/06 // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C07C 315/00 315/06 // C07B 61/00 300
Claims (4)
た粗製の２,４'−ジヒドロキシジフェニルスルホン類を
精製して、高純度の２,４'−ジヒドロキシジフェニルス
ルホン類を製造するに当たり、精製溶媒として、低級脂
肪族アルコール類の中から選ばれた少なくとも１種５〜
２０重量％と非ハロゲン系芳香族炭化水素類の中から選
ばれた少なくとも１種９５〜８０重量％とから成る混合
溶媒を用い、処理することを特徴とする高純度２,４'−
ジヒドロキシジフェニルスルホン類の製造方法。1. Purification of crude 2,4′-dihydroxydiphenylsulfones obtained by the reaction of phenols and sulfuric acid to produce high-purity 2,4′-dihydroxydiphenylsulfones. At least one selected from lower aliphatic alcohols as a solvent 5
High-purity 2,4'-characterized in that treatment is carried out using a mixed solvent consisting of 20% by weight and 95-80% by weight of at least one selected from non-halogenated aromatic hydrocarbons.
A method for producing dihydroxydiphenyl sulfones.
た粗製の２,４'−ジヒドロキシジフェニルスルホン類を
精製して、高純度の２,４'−ジヒドロキシジフェニルス
ルホン類を製造するに当たり、精製溶媒として、ケトン
類の中から選ばれた少なくとも１種１０〜４０重量％と
非ハロゲン系芳香族炭化水素類の中から選ばれた少なく
とも１種９０〜６０重量％とから成る混合溶媒を用い、
処理することを特徴とする高純度２,４'−ジヒドロキシ
ジフェニルスルホン類の製造方法。2. Purification of crude 2,4′-dihydroxydiphenylsulfones obtained by the reaction of phenols and sulfuric acid to produce high-purity 2,4′-dihydroxydiphenylsulfones. As the solvent, a mixed solvent consisting of 10 to 40% by weight of at least one kind selected from ketones and 90 to 60% by weight of at least one kind selected from non-halogenated aromatic hydrocarbons is used,
A method for producing high-purity 2,4′-dihydroxydiphenylsulfones, which comprises treating.
た粗製の２,４'−ジヒドロキシジフェニルスルホン類を
精製して、高純度の２,４'−ジヒドロキシジフェニルス
ルホン類を製造するに当たり、精製溶媒として、酢酸エ
ステル類の中から選ばれた少なくとも１種１０〜４０重
量％と非ハロゲン系芳香族炭化水素類の中から選ばれた
少なくとも１種９０〜６０重量％とから成る混合溶媒を
用い、処理することを特徴とする高純度２,４'−ジヒド
ロキシジフェニルスルホン類の製造方法。3. Purification of crude 2,4′-dihydroxydiphenylsulfones obtained by the reaction of phenols and sulfuric acid to produce high-purity 2,4′-dihydroxydiphenylsulfones. As the solvent, a mixed solvent of 10 to 40% by weight of at least one selected from acetic acid esters and 90 to 60% by weight of at least one selected from non-halogenated aromatic hydrocarbons is used. A method for producing high-purity 2,4′-dihydroxydiphenylsulfones, which comprises treating
類が、フェノールを原料として得られる２,４'−ジヒド
ロキシジフェニルスルホンである請求項１、２又は３記
載の高純度２,４'−ジヒドロキシジフェニルスルホン類
の製造方法。4. The highly pure 2,4′-dihydroxydiphenyl according to claim 1, 2 or 3, wherein the 2,4′-dihydroxydiphenyl sulfone is 2,4′-dihydroxydiphenyl sulfone obtained from phenol as a raw material. Method for producing sulfones.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5152921A JPH07119196B2 (en) | 1992-06-12 | 1993-05-31 | Method for producing high-purity 2,4'-dihydroxydiphenyl sulfones |
| US08/164,855 US5399772A (en) | 1993-05-31 | 1993-12-10 | Method of producing A 2,4'-dihydroxydiphenylsulfone |
| EP93120018A EP0627415B1 (en) | 1993-05-31 | 1993-12-11 | A method of producing a 2,4'-dihydroxydiphenylsulfone |
| DE69313832T DE69313832T2 (en) | 1993-05-31 | 1993-12-11 | Process for the preparation of 2,4-dihydroxydiphenyl sulfone |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-179003 | 1992-06-12 | ||
| JP17900392 | 1992-06-12 | ||
| JP5152921A JPH07119196B2 (en) | 1992-06-12 | 1993-05-31 | Method for producing high-purity 2,4'-dihydroxydiphenyl sulfones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06107623A true JPH06107623A (en) | 1994-04-19 |
| JPH07119196B2 JPH07119196B2 (en) | 1995-12-20 |
Family
ID=26481701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5152921A Expired - Fee Related JPH07119196B2 (en) | 1992-06-12 | 1993-05-31 | Method for producing high-purity 2,4'-dihydroxydiphenyl sulfones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07119196B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998051511A1 (en) * | 1997-05-14 | 1998-11-19 | Nippon Kayaku Kabushiki Kaisha | Thermal recording material and novel crystal of bisphenol s derivative |
| JP2002088053A (en) * | 2000-09-08 | 2002-03-27 | Nippon Soda Co Ltd | Method for producing 4,4'-bisphenolsulfone |
| JP2002145851A (en) * | 2000-11-10 | 2002-05-22 | Nippon Soda Co Ltd | Method of producing 4,4'-bisphenol sulfone |
| JP2003104954A (en) * | 2001-09-28 | 2003-04-09 | Konishi Kagaku Ind Co Ltd | Method for producing dihydroxydiphenylsulfone isomer mixture |
| JP2003104956A (en) * | 2001-09-28 | 2003-04-09 | Konishi Kagaku Ind Co Ltd | Method for producing dihydroxydiphenylsulfone isomer mixture |
-
1993
- 1993-05-31 JP JP5152921A patent/JPH07119196B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998051511A1 (en) * | 1997-05-14 | 1998-11-19 | Nippon Kayaku Kabushiki Kaisha | Thermal recording material and novel crystal of bisphenol s derivative |
| US6114282A (en) * | 1997-05-14 | 2000-09-05 | Nippon Kayaku Kabushiki Kaisha | Thermal recording material and novel crystal of bisphenol S derivative |
| JP2002088053A (en) * | 2000-09-08 | 2002-03-27 | Nippon Soda Co Ltd | Method for producing 4,4'-bisphenolsulfone |
| JP2002145851A (en) * | 2000-11-10 | 2002-05-22 | Nippon Soda Co Ltd | Method of producing 4,4'-bisphenol sulfone |
| JP2003104954A (en) * | 2001-09-28 | 2003-04-09 | Konishi Kagaku Ind Co Ltd | Method for producing dihydroxydiphenylsulfone isomer mixture |
| JP2003104956A (en) * | 2001-09-28 | 2003-04-09 | Konishi Kagaku Ind Co Ltd | Method for producing dihydroxydiphenylsulfone isomer mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07119196B2 (en) | 1995-12-20 |
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