JPH06107622A - Production of 2,4'-dihydroxydiphenyl sulfones - Google Patents
Production of 2,4'-dihydroxydiphenyl sulfonesInfo
- Publication number
- JPH06107622A JPH06107622A JP5152920A JP15292093A JPH06107622A JP H06107622 A JPH06107622 A JP H06107622A JP 5152920 A JP5152920 A JP 5152920A JP 15292093 A JP15292093 A JP 15292093A JP H06107622 A JPH06107622 A JP H06107622A
- Authority
- JP
- Japan
- Prior art keywords
- dihydroxydiphenyl
- reaction
- producing
- sulfones
- phenol
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は2,4'−ジヒドロキシジ
フェニルスルホン類の新規な製造方法に関するものであ
る。さらに詳しくいえば、本発明は、感熱紙用顕色剤な
どとして有用な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から高い選択率で効率よく
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 novel method for producing 2,4'-dihydroxydiphenyl sulfones. More specifically, the present invention relates to a method for efficiently producing 2,4′-dihydroxydiphenyl sulfones useful as a color developer for thermal papers with a high selectivity from phenols and sulfuric acid.
【0002】[0002]
【従来の技術】従来、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おり、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、従
来、4,4'−ジヒドロキシジフェニルスルホン類の製造
方法については、様々な試みがなされ、異性体である
2,4'−ジヒドロキシジフェニルスルホン類の生成を極
力少なくして、純度の高い4,4'−ジヒドロキシジフェ
ニルスルホン類を得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収率を高める製造
方法については、これまで報告がなされていないのが実
状である。2. Description of the Related Art Conventionally, various phenol compounds have been developed as a color developer for thermal paper, and among them, 2,4'-
Dihydroxydiphenyl sulfones are expected as extremely useful developers for thermal paper. However, various attempts have hitherto been made regarding the method for producing 4,4′-dihydroxydiphenylsulfones, and the production of isomers 2,4′-dihydroxydiphenylsulfones is minimized to obtain highly pure 4 Efforts have been made to obtain 4,4'-dihydroxydiphenyl sulfones, but 2,4'-
The fact is that no report has been made so far regarding a production method for increasing the yield 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、感熱紙用顕色剤などとして有用な2,4'
−ジヒドロキシジフェニルスルホン類を高い選択率で工
業的に有利に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 these circumstances, the present invention is useful as a developer for thermal paper, etc.
The present invention has been made for the purpose of providing a method for industrially advantageously producing dihydroxydiphenyl sulfones with a high selectivity.
【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、反応系に特定
の触媒を存在させ、無溶媒下又は特定の溶媒の存在下
に、フェノール類と硫酸とを加熱することにより、2,
4'−ジヒドロキシジフェニルスルホン類が高い選択率
で得られ、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を混合し、加熱して
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、触媒としてホスホン酸、ホスフィン酸及びそ
れらの塩の中から選ばれた少なくとも1種を反応系に存
在させ、無溶媒下又は常圧での沸点が130〜200℃
の芳香族炭化水素溶媒の存在下に反応を行うことを特徴
とする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 As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a specific catalyst is allowed to exist in a reaction system, and it is used in the absence of solvent or in the presence of a specific solvent. By heating phenols and sulfuric acid,
It was found that 4′-dihydroxydiphenyl sulfones can be obtained with a high selectivity and the purpose thereof can be achieved, and the present invention has been completed based on this finding. That is,
According to the present invention, at least one kind selected from phosphonic acid, phosphinic acid and salts thereof is used as a catalyst in producing 2,4′-dihydroxydiphenylsulfones by mixing phenols and sulfuric acid and heating. Is present in the reaction system and has a boiling point of 130 to 200 ° C. under no solvent or at normal pressure.
The present invention provides a method for producing 2,4′-dihydroxydiphenylsulfones, which comprises performing the reaction in the presence of the aromatic hydrocarbon solvent.
【0005】以下、本発明を詳細に説明する。本発明に
おいて、原料として用いられる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。本発明方法においては、無溶媒下又
は沸点が130〜200℃の芳香族炭化水素溶媒中にお
いて加熱し、反応させるが、この際触媒として、ホスホ
ン酸、ホスフィン酸及びこれらの塩の中から選ばれた少
なくとも1種を反応系に存在させることが必要である。
該触媒の使用量は、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。この触媒の
量が2重量%未満では2,4'−ジヒドロキシジフェニル
スルホン類の選択率の向上効果が十分に発揮されない
し、10重量%を超えるとその量の割には2,4'−ジヒ
ドロキシジフェニルスルホン類の選択率の向上があまり
認められない。The present invention will be described in detail below. In the present invention, as the phenols used as the raw material,
For example, phenol, o-cresol, m-cresol,
2,3-xylenol, 2,5-xylenol, 3,5-
At least one ortho- and para-position such as xylenol, or a mixture of two or more selected from the phenols having no substitution, or one selected from these phenols and p-cresol, Mention may be made, for example, of a mixture of 2,4-xylenol, 2,6-xylenol, 3,4-xylenol and the like, which is selected from two ortho- or para-substituted phenols. 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. In the method of the present invention, the reaction is carried out by heating without solvent or in an aromatic hydrocarbon solvent having a boiling point of 130 to 200 ° C., and at this time, the catalyst is selected from phosphonic acid, phosphinic acid and salts thereof. It is necessary that at least one kind is present in the reaction system.
The amount of the catalyst used is usually 2% by weight or more, preferably 5 to 10% by weight, based on sulfuric acid. If the amount of this catalyst is less than 2% by weight, the effect of improving the selectivity of 2,4'-dihydroxydiphenylsulfones is not sufficiently exerted, and if it exceeds 10% by weight, the amount of 2,4'-dihydroxy sulfone is 2,4'-dihydroxy. No significant improvement in the selectivity of diphenyl sulfones is observed.
【0006】溶媒を用いずに反応を行う場合は、減圧
下、好ましくは600〜50mmHgの減圧下に、140〜
170℃の範囲の温度で加熱して反応させるのが望まし
い。また、溶媒の存在下に反応を行う場合は、反応溶媒
として、常圧での沸点が130〜200℃の範囲にある
芳香族炭化水素が用いられる。該芳香族炭化水素として
は、例えばキシレン、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、Shellsol A[シェル
化学社製、商品名]、Shellsol AB[シェル
化学社製、商品名]などが挙げられ、これらは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。ま
た常圧での沸点が130〜200℃の範囲にある芳香族
石油溶剤を用いることもできる。これらの溶剤を用いて
反応を行う場合、通常常圧下又は弱減圧下に、反応生成
水を共沸により、反応系外に留去させながら反応させる
方法が用いられる。このような溶媒を用いる方法におい
ては、反応終了後、副生成物であるフェノールスルホン
酸類は中和することなくろ過によって容易にジヒドロキ
シジフェニルスルホン類と分離することができ、該フェ
ノールスルホン酸類と溶媒とは再利用することができ
る。When the reaction is carried out without using a solvent, it is carried out under reduced pressure, preferably under reduced pressure of 600-50 mmHg, at 140-
It is desirable to heat and react at a temperature in the range of 170 ° C. When the reaction is carried out in the presence of a solvent, an aromatic hydrocarbon having a boiling point of 130 to 200 ° C. at atmospheric pressure is used as the reaction solvent. Examples of the aromatic hydrocarbon include xylene, ethylbenzene, butylbenzene, diethylbenzene, mesitylene, cymene, cumene, pseudocumene, Shellsol A [trade name, manufactured by Shell Chemical Co., Ltd.], Shellsol AB [trade name, manufactured by Shell Chemical Company, etc.] These may be used alone or in combination of two or more. It is also possible to use an aromatic petroleum solvent having a boiling point in the range of 130 to 200 ° C at atmospheric pressure. When the reaction is carried out using these solvents, a method is generally used in which the reaction product water is azeotropically distilled off under normal pressure or weak pressure while being distilled out of the reaction system. In the method using such a solvent, after the reaction is completed, the by-product phenolsulfonic acid can be easily separated from the dihydroxydiphenylsulfone by filtration without neutralization, and the phenolsulfonic acid and the solvent can be separated from each other. Can be reused.
【0007】従来の4,4'−ジヒドロキシジフェニルス
ルホンの製造方法においては、ジヒドロキシジフェニル
スルホン異性体混合物を80モル%以上の収率で得よう
とした場合、副生する2,4'−ジヒドロキシジフェニル
スルホンの生成率は、約20重量%以下に抑えられてし
まい、一方、2,4'−ジヒドロキシジフェニルスルホン
の生成率を20重量%以上に高めようとすれば、ジヒド
ロキシジフェニルスルホン異性体混合物の収率を80モ
ル%以下に抑えなければならず、このような従来法を
2,4'−ジヒドロキシジフェニルスルホン類の製造に適
用するには、経済的に極めて不利であった。これに対
し、本発明の製造方法によれば、例えばフェノールを原
料とする場合、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
比率を重量比50:50近くまで高めることができ、し
かもジヒドロキシジフェニルスルホン異性体混合物の収
率も80モル%以上に高めることができる。また、原料
として、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
の生成比率を80重量%以上に高めることができ、しか
もジヒドロキシジフェニルスルホン誘導体の異性体混合
物の収率も80モル%以上に高めることができる。本発
明方法により得られたジヒドロキシジフェニルスルホン
類の異性体混合物は、所望により、適当な精製法、例え
ば溶媒を用いる精製法などによって、さらに高純度の
2,4'−ジヒドロキシジフェニルスルホン類に精製する
ことができる。In the conventional method for producing 4,4'-dihydroxydiphenylsulfone, when it is attempted to obtain a dihydroxydiphenylsulfone isomer mixture in a yield of 80 mol% or more, 2,4'-dihydroxydiphenyl produced as a by-product. The production rate of sulfone is suppressed to about 20% by weight or less. On the other hand, if the production rate of 2,4′-dihydroxydiphenylsulfone is increased to 20% by weight or more, the yield of the dihydroxydiphenylsulfone isomer mixture is reduced. Therefore, it is economically extremely disadvantageous to apply such a conventional method to the production of 2,4'-dihydroxydiphenyl sulfones. On the other hand, according to the production method of the present invention, for example, when phenol is used as a raw material, the production ratio of 2,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxydiphenylsulfone is close to 50:50 by weight. The yield of the dihydroxydiphenyl sulfone isomer mixture can be increased to 80 mol% or more. Further, when 5-methyl-2,4'-dihydroxydiphenyl sulfone is produced using phenol and p-cresol as a raw material, or 3,5-dimethyl-2,4 is produced using phenol and 2,4-xylenol. In the case of producing'-dihydroxydiphenylsulfone, the production ratio of 2,4'-dihydroxy compound can be increased to 80% by weight or more, and the yield of the isomer mixture of dihydroxydiphenylsulfone derivative can be increased to 80% by mole or more. be able to. If desired, the isomer mixture of dihydroxydiphenylsulfones obtained by the method of the present invention is further purified to a highly pure 2,4′-dihydroxydiphenylsulfone by a suitable purification method, for example, a purification method using a solvent. be able to.
【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 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。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 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. When 250 g of effluent was obtained, 165 g of phenol was added. Add 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.
【0009】実施例2 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。 実施例3 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。 実施例4 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。Example 2 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 to 165 ° C. for 3 hours under a reduced pressure of 560 to 260 mmHg to obtain 240 g of effluent. Add 165 g of phenol and 2
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. Example 3 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, a dehydration reaction was carried out under reflux for 6 hours, and then the mixture was cooled to room temperature and filtered to remove phenolsulfonic acid. 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. Example 4 Phenol 793 g, sulfuric acid 334 g, Shel in a reactor
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.
【0010】実施例5 反応器にフェノール793g、硫酸334g、Shel
lsol AB940g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、所定の脱水量を得
た。この反応液を室温まで冷却し、析出した結晶をろ過
洗浄し、乾燥した。ろ液を中和洗浄し、脱溶媒後乾燥し
結晶を得た。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51wt%、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2wt%の組成
であった。 実施例6 反応器にp−クレゾール368g、硫酸334g、Sh
ellsol A2000ミリリットル及びホスホン酸
16.5gを仕込み、還流下2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。次に、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81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、
5−メチル−2,4'−ジヒドロキシジフェニルスルホン
(mp.179℃)が90wt%、その他成分が10wt%
の組成であった。 実施例7 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。EXAMPLE 5 Phenol 793 g, sulfuric acid 334 g, Shel were placed in a reactor.
940 g of lsol AB and 16.5 g of phosphonic acid were charged and dehydration reaction was carried out under reflux for 6 hours to obtain a predetermined dehydration amount. The reaction solution was cooled to room temperature, and the precipitated crystals were washed by filtration and dried. The filtrate was neutralized and washed, desolvated and dried to give crystals. A dihydroxydiphenyl sulfone isomer mixture was obtained with a yield of 82 mol%. As a result of analysis by high performance liquid chromatography, the composition was 51% by weight of 2,4'-dihydroxydiphenylsulfone, 47% by weight of 4,4'-dihydroxydiphenylsulfone, and 2% by weight of other components. Example 6 p-Cresol 368 g, sulfuric acid 334 g, Sh
2000 ml of ellsol A and 16.5 g of phosphonic acid were charged, dehydration reaction was carried out under reflux for 2 hours, and then 384 g of phenol was added and dehydration reaction was carried out for 4 hours. Next, the mixture was cooled 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 81 mol%. As a result of analysis by high performance liquid chromatography,
90 wt% of 5-methyl-2,4'-dihydroxydiphenyl sulfone (mp.179 ° C), 10 wt% of other components
The composition was. Example 7 2,4-xylenol (416 g) and sulfuric acid (334 g) 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%.
【0011】比較例1 反応器にフェノール628g、硫酸334g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160gを得たところで、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120gを得た。さらに
フェノール120gを加え260〜100mmHgの減圧下
2時間脱水反応を行い流出物が90g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76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18wt%、4,4'−ジヒドロキ
シジフェニルスルホンが77wt%、その他成分が5wt%
の組成であった。Comparative Example 1 A reactor was charged with 628 g of phenol and 334 g of sulfuric acid,
Under a reduced pressure of 560 to 260 mmHg, dehydration reaction was performed at 150 to 165 ° C. for 3 hours, and when effluent 160 g was obtained, 165 g of phenol was added and a reduced pressure of 260 to 100 mmHg,
The dehydration reaction was performed for 2 hours to obtain 120 g of effluent. Further, 120 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 reached 90 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 76 mol%. High-performance liquid chromatography analysis revealed that 2,4'-dihydroxydiphenyl sulfone was 18 wt%, 4,4'-dihydroxydiphenyl sulfone was 77 wt%, and other components were 5 wt%.
The composition was.
【0012】[0012]
【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、2,4'−ジヒドロキシジフェニルスルホン類
が高い選択率で収率よく得られる。該2,4'−ジヒドロ
キシジフェニルスルホン類は、ジアリールジヒドロキシ
ジフェニルスルホンや4−イソプロポキシ−4'−ヒド
ロキシジフェニルスルホンに替わりうる保存性の良い感
熱紙用顕色剤として有用である。According to the method of the present invention, 2,4'-dihydroxydiphenyl sulfones can be obtained in high yield from phenols and sulfuric acid with high selectivity. The 2,4′-dihydroxydiphenyl sulfones are useful as a developer having good storage stability and can replace diaryldihydroxydiphenyl sulfones and 4-isopropoxy-4′-hydroxydiphenyl sulfones.
───────────────────────────────────────────────────── 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 // C07B 61/00 300 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location // C07B 61/00 300
Claims (6)
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、触媒としてホスホン酸、ホスフィン酸及びそ
れらの塩の中から選ばれた少なくとも1種を反応系に存
在させ、無溶媒下又は常圧での沸点が130〜200℃
の芳香族炭化水素溶媒の存在下に反応を行うことを特徴
とする2,4'−ジヒドロキシジフェニルスルホン類の製
造方法。1. At least one selected from phosphonic acid, phosphinic acid and salts thereof as a catalyst when 2,4'-dihydroxydiphenyl sulfone is produced by mixing phenols and sulfuric acid and heating them. The seed is present in the reaction system and has a boiling point of 130 to 200 ° C. without a solvent or at normal pressure.
The method for producing 2,4′-dihydroxydiphenyl sulfones, which comprises performing the reaction in the presence of the aromatic hydrocarbon solvent.
の温度に加熱して反応を行う請求項1記載の2,4'−ジ
ヒドロキシジフェニルスルホン類の製造方法。2. A solvent-free, 140-170 ° C. under reduced pressure.
The method for producing 2,4′-dihydroxydiphenylsulfones according to claim 1, wherein the reaction is carried out by heating to the temperature of.
炭化水素溶媒を用い、反応生成水を共沸により系外へ留
去させながら反応を行う請求項1記載の2,4'−ジヒド
ロキシジフェニルスルホン類の製造方法。3. The 2,4 ′ according to claim 1, wherein the reaction is carried out by using an aromatic hydrocarbon solvent having a boiling point of 130 to 200 ° C. at atmospheric pressure and distilling out the water produced by the reaction by azeotropic distillation. -Method for producing dihydroxydiphenyl sulfones.
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 2,4′-dihydroxydiphenyl sulfone according to claim 1, 2 or 3 which is 2,4′-dihydroxydiphenyl sulfone obtained from phenol as a raw material. Manufacturing method.
類が、フェノールとp−クレゾールとを原料として得ら
れる5−メチル−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2,4'−ジヒドロ
キシジフェニルスルホン類の製造方法。5. The 2,4′-dihydroxydiphenyl sulfone is 5-methyl-2,4′-dihydroxydiphenyl sulfone obtained by using phenol and p-cresol as raw materials. A method for producing 2,4'-dihydroxydiphenyl sulfones.
類が、フェノールと2,4−キシレノールとを原料とし
て得られる3,5−ジメチル−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2,
4'−ジヒドロキシジフェニルスルホン類の製造方法。6. The 2,4′-dihydroxydiphenyl sulfone is 3,5-dimethyl-2,4′-dihydroxydiphenyl sulfone obtained by using phenol and 2,4-xylenol as raw materials. Or 2 of 3,
A method for producing 4'-dihydroxydiphenyl sulfones.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5152920A JPH07119195B2 (en) | 1992-06-12 | 1993-05-31 | Method for producing 2,4'-dihydroxydiphenyl sulfones |
US08/164,855 US5399772A (en) | 1993-05-31 | 1993-12-10 | 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 |
EP93120018A EP0627415B1 (en) | 1993-05-31 | 1993-12-11 | A method of producing a 2,4'-dihydroxydiphenylsulfone |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17900392 | 1992-06-12 | ||
JP4-179003 | 1992-06-12 | ||
JP5152920A JPH07119195B2 (en) | 1992-06-12 | 1993-05-31 | Method for producing 2,4'-dihydroxydiphenyl sulfones |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06107622A true JPH06107622A (en) | 1994-04-19 |
JPH07119195B2 JPH07119195B2 (en) | 1995-12-20 |
Family
ID=26481700
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5152920A Expired - Fee Related JPH07119195B2 (en) | 1992-06-12 | 1993-05-31 | Method for producing 2,4'-dihydroxydiphenyl sulfones |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07119195B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003104955A (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 |
WO2003070695A1 (en) * | 2002-02-22 | 2003-08-28 | Konishi Chemical Ind. Co., Ltd. | Processes for production of dihydroxydiphenyl sulfone isomeric mixtures |
-
1993
- 1993-05-31 JP JP5152920A patent/JPH07119195B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003104955A (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 |
WO2003070695A1 (en) * | 2002-02-22 | 2003-08-28 | Konishi Chemical Ind. Co., Ltd. | Processes for production of dihydroxydiphenyl sulfone isomeric mixtures |
Also Published As
Publication number | Publication date |
---|---|
JPH07119195B2 (en) | 1995-12-20 |
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