JPH02250861A - Production of 4,4'-dihydroxydiphenylsulfone - Google Patents
Production of 4,4'-dihydroxydiphenylsulfoneInfo
- Publication number
- JPH02250861A JPH02250861A JP6916289A JP6916289A JPH02250861A JP H02250861 A JPH02250861 A JP H02250861A JP 6916289 A JP6916289 A JP 6916289A JP 6916289 A JP6916289 A JP 6916289A JP H02250861 A JPH02250861 A JP H02250861A
- Authority
- JP
- Japan
- Prior art keywords
- water
- dihydroxydiphenylsulfone
- reaction
- sulfone
- hydroxide
- 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000006317 isomerization reaction Methods 0.000 abstract description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000003457 sulfones Chemical class 0.000 description 6
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- LFASIQLVFCSCCU-UHFFFAOYSA-N 4-(4-chlorophenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 LFASIQLVFCSCCU-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、４．４’−ジヒドロキシジフェニルスルホン
の製造法に関するものである。さらに詳しくは、本発明
は、４．４′−ジクロロジフェニルスルホンを加水分解
することによって、４・４′−ジヒドロキシジフェニル
スルホンを製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 4,4'-dihydroxydiphenyl sulfone. More specifically, the present invention relates to a method for producing 4,4'-dihydroxydiphenyl sulfone by hydrolyzing 4,4'-dichlorodiphenyl sulfone.
４、ｓ’−ジヒドロキシジフェニルスルホンの合成に関
しては、従来から、さまざまな試みがなされている。た
とえば、米国特許第３．２９７．７６６号には、フェノ
ールと硫酸を反応させることによって、ジヒドロキシジ
フェニルスルホンを合成する方法が述べられているが、
単にフェノールと硫酸を反応させることによって得られ
るジヒドロキシジフェニルスルホンは、４．４’−ジヒ
ドロキシジフェニルスルホンと２．４′−ジヒドロキシ
ジフェニルスルホンの異性体混合物であり、純度の高い
４，４′−ジヒドロキシジフェニルスルホンを得るため
には、２つの異性体を分離したり、あるいは２，４′−
ジヒドロキシジフェニルスルホンを４．４’ −ジヒド
ロキシジフェニルスルホンに異性化するという工程を特
徴とする
特公昭第６０−３３３８３号公報には、フェノールと三
酸化硫黄とを液状フッ化水素の存在下で反応させること
からなる、４．４’−ジヒドロキシジフェニルスルホン
の製造方法が提案されている。この反応には、加圧容器
を必要とする上に、三酸化硫黄もフッ化水素も腐食性の
強い化合物であるので、実施には多くの困難を伴う。Various attempts have been made to synthesize 4,s'-dihydroxydiphenyl sulfone. For example, U.S. Pat. No. 3,297,766 describes a method for synthesizing dihydroxydiphenyl sulfone by reacting phenol with sulfuric acid.
Dihydroxydiphenylsulfone obtained by simply reacting phenol with sulfuric acid is an isomer mixture of 4,4'-dihydroxydiphenylsulfone and 2,4'-dihydroxydiphenylsulfone, and is highly pure 4,4'-dihydroxydiphenyl. To obtain the sulfone, the two isomers can be separated or the 2,4'-
Japanese Patent Publication No. 60-33383, which features a process of isomerizing dihydroxydiphenylsulfone to 4,4'-dihydroxydiphenylsulfone, describes a process in which phenol and sulfur trioxide are reacted in the presence of liquid hydrogen fluoride. A method for producing 4,4'-dihydroxydiphenyl sulfone has been proposed. This reaction requires a pressurized container and is accompanied by many difficulties in implementation, as both sulfur trioxide and hydrogen fluoride are highly corrosive compounds.
米国特許第４．０８９．９０４号には、４．４′−チオ
ジフェノールを酸化して、４．４’−ジヒドロキシジフ
ェニルスルホンを得る方法が開示されている。しかし、
この酸化には、酸化剤としての過酸化水素や、モリブデ
ン酸系触媒のような高価な原料を必要とするので、経済
的に実施し得るとは言いがたい。U.S. Pat. No. 4,089,904 discloses a method for oxidizing 4,4'-thiodiphenol to obtain 4,4'-dihydroxydiphenyl sulfone. but,
Since this oxidation requires expensive raw materials such as hydrogen peroxide as an oxidizing agent and a molybdic acid catalyst, it is difficult to say that it can be carried out economically.
１９７２年発行の、ジュルナーノペオルガニーチェスコ
イ、ヒーミイ、第８巻、５９７−６００頁には、４□４
′−ジクロロジフェニルスルホンに過剰量の水酸化ナト
リウム水溶液を加えて、２２０℃で加水分解し、４．４
’−ジヒドロキシジフェニルスルホンを得る方法が述べ
られている。この方法によれば、フェノールと硫酸の反
応による場合のように異性体を生ずることなく、４．４
′−ジヒドロキシジフェニルスルホンが得られるが、水
酸化ナトリウムの水溶液を用いて高温で反応するため、
加圧容器が必要であり、工業的に容易には実施し難い。4□4 in Jurnanopeorganycheskoy, Himii, Vol. 8, pp. 597-600, published in 1972.
'-Dichlorodiphenylsulfone was added with an excess amount of sodium hydroxide aqueous solution and hydrolyzed at 220°C to give 4.4
A method for obtaining '-dihydroxydiphenylsulfone is described. According to this method, 4.4
'-Dihydroxydiphenylsulfone is obtained, but because the reaction is performed at high temperature using an aqueous solution of sodium hydroxide,
This method requires a pressurized container and is difficult to implement industrially.
４．４′−ジクロロジフェニルスルホンを常圧下で加水
分解しようとする試みもなされている。Attempts have also been made to hydrolyze 4.4'-dichlorodiphenyl sulfone under normal pressure.
たとえば、１９８１年発行のイズヴエスチャ、ヴイスシ
フ、ウチェブニフ、ザヴエジェニー、ヒーミャ、イ、ヒ
ミーチェスカヤ、チクノロギヤ、第２４巻、１０８５−
１０９０頁には、４．４′−ジクロロジフェニルスルホ
ンの水和ジメチルスルホキシド中での水酸化ナトリウム
による加水分解が報告されているが、反応は１個の塩素
原子のみが置換された、４−クロロ−４′−ヒドロキシ
ジフェニルスルホンまでしか進んでいない。For example, published in 1981 in Izvuescha, Vyssiv, Uchebniv, Zavezheni, Himya, I, Himicheskaya, Tiknologia, Volume 24, 1085-
On page 1090, the hydrolysis of 4,4'-dichlorodiphenyl sulfone with sodium hydroxide in hydrated dimethyl sulfoxide is reported, but the reaction is similar to that of 4-chloro, in which only one chlorine atom has been replaced. It has only progressed to -4'-hydroxydiphenyl sulfone.
本発明者等は、工業的に容易に人手し得る原料である４
、４′−ジクロロジフェニルスルホンを原料として、常
圧下の反応により、４．４′−ジヒドロキシジフェニル
スルホンを高純度かつ高収率で製造する方法を種々検討
した結果、４．４′−ジクロロジフエニルスルホンを特
定組成の溶媒中で、特定量のアルカリ金属水酸化物を用
いて加水分解することにより、反応が円滑に進行して、
４．４′−ジヒドロキシジフェニルスルホンが得られる
ことを見出し、本発明に到達したものである。The present inventors have discovered that 4 is a raw material that can be easily produced industrially by hand.
As a result of various studies on methods for producing 4,4'-dihydroxydiphenyl sulfone with high purity and high yield by reaction under normal pressure using 4'-dichlorodiphenyl sulfone as a raw material, we found that 4,4'-dichlorodiphenyl By hydrolyzing sulfone using a specific amount of alkali metal hydroxide in a solvent with a specific composition, the reaction proceeds smoothly.
It was discovered that 4,4'-dihydroxydiphenyl sulfone can be obtained, and the present invention was achieved.
本発明は、４．４’−ジクロロジフェニルスルホンをジ
メチルスルホキシド／水の重量比が５０１５０以上９５
１５未満であるジメチルスルホキシド／水混合溶媒中に
おいて、４．４’−ジクロロジフェニルスルホン１モル
当り５モル以上１５モル未満の水酸化リチウム、水酸化
ナトリウムおよび水酸化カリウムよりなる群より選ばれ
た１種以上の化合物を加えて加水分解することを特徴と
する、４．４′−ジヒドロキシジフェニルスルホンの製
造方法である。The present invention provides 4,4'-dichlorodiphenyl sulfone with a dimethyl sulfoxide/water weight ratio of 50150 or more and 95
1 selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide in an amount of 5 mol or more and less than 15 mol per 1 mol of 4.4'-dichlorodiphenyl sulfone in a dimethyl sulfoxide/water mixed solvent of less than 15 This is a method for producing 4,4'-dihydroxydiphenyl sulfone, which is characterized by adding and hydrolyzing more than one type of compound.
ステンレス鋼などの耐アルカリ性容器に、４・４′−ジ
クロロジフェニルスルホン、ジメチルスルホキシド、水
、およびアルカリ金属水酸化物を仕込み、撹拌しながら
加熱する。最初は、４．４′−ジクロロジフェニルスル
ホンが液体中に分散しているが、温度が上昇すると、４
．４′−ジクロロジフェニルスルホンは溶解し、反応混
合物は液−液２相系となり、やがてアルカリ金属塩化物
の析出が始まる。4,4'-dichlorodiphenyl sulfone, dimethyl sulfoxide, water, and alkali metal hydroxide are placed in an alkali-resistant container such as stainless steel, and heated while stirring. Initially, 4,4'-dichlorodiphenylsulfone is dispersed in the liquid, but as the temperature increases, 4,4'-dichlorodiphenylsulfone is dispersed in the liquid.
．． 4'-dichlorodiphenylsulfone is dissolved, the reaction mixture becomes a liquid-liquid two-phase system, and soon precipitation of alkali metal chloride begins.
反応に用いるジメチルスルホキシド／水の重量比は、５
０１５０以上９５１５未満、好ましくは、６０／４０以
上８０／２０未満である。ジメチルスルホキシド／水の
重量比が５０１５０未満であると、反応を長時間性なっ
ても加水分解は完全に進行せず、主生成ｍは４−クロロ
−４′−ヒドロキシジフェニルスルホンである。また、
ジメチルスルホキシド／水の重量比が９５１５以上にな
っても、反応速度はかえって遅くなる。The weight ratio of dimethyl sulfoxide/water used in the reaction was 5.
0150 or more and less than 9515, preferably 60/40 or more and less than 80/20. If the weight ratio of dimethyl sulfoxide/water is less than 50,150, hydrolysis will not proceed completely even if the reaction is carried out for a long time, and the main product m will be 4-chloro-4'-hydroxydiphenyl sulfone. Also,
Even if the weight ratio of dimethyl sulfoxide/water is 9515 or more, the reaction rate is rather slow.
アルカリ金属の水酸化物は、水酸化リチウム、水酸化ナ
トリウム、水酸化カリウムの中から任意に選ぶことがで
きるし、またこれらの２種以上を併用することもできる
。反応に必要なアルカリ金属水酸化物の量は、４．４’
−ジクロロジフェニルスルホン１モル当り５モル以上１
５モル未満である。ジメチルスルホキシド／水の重量比
が大きいほど、使用するアルカリ金属水酸化物の量は少
なくてよいが、４．４’−ジクロロジフェニルスルホン
１モル当りのアルカリ金属水酸化物の量が５モル未満で
あると、ジメチルスルホキシド／水の重量比を大きくし
ても得られる４、４′−ジヒドロキシジフェニルスルホ
ンの量は増加せず、構造不明の副生物が生成する。４．
４′−ジクロロジフェニルスルホン１モル当りのアルカ
リ金属水酸化物の量を１５モル以上とした場合も、副生
物の生成が多くなるので好ましくない。The alkali metal hydroxide can be arbitrarily selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide, or two or more of these can be used in combination. The amount of alkali metal hydroxide required for the reaction is 4.4'
-5 moles or more 1 per mole of dichlorodiphenyl sulfone
Less than 5 moles. The higher the weight ratio of dimethyl sulfoxide/water, the lower the amount of alkali metal hydroxide used, but if the amount of alkali metal hydroxide is less than 5 moles per mole of 4,4'-dichlorodiphenyl sulfone, If so, the amount of 4,4'-dihydroxydiphenyl sulfone obtained will not increase even if the weight ratio of dimethyl sulfoxide/water is increased, and a by-product of unknown structure will be produced. 4.
It is also undesirable to increase the amount of alkali metal hydroxide per mole of 4'-dichlorodiphenylsulfone to 15 moles or more because by-products will be produced in large quantities.
反応温度は、１４０℃以上かつ常圧における反応混合物
の沸点以下、すなわち、混合溶媒に４．４′−ジクロロ
ジフェニルスルホンおよびアルカリ金属水酸化物を加え
た混合物の沸点以下である。ジメチルスルホキシド／水
の重量比５０１５０の混合溶媒の沸点は約１０９℃であ
り、９５１５の混合溶媒の沸点は約１６３℃であるが、
混合溶媒に４．４′ジクロロジフエニルスルホンおよび
アルカリ金属水酸化物を加えた混合物は、最初、混合溶
媒の沸点よりはるかに高い温度で沸騰し、その後反応の
進行につれて、沸騰温度は徐々に下がってくる。The reaction temperature is 140°C or higher and lower than the boiling point of the reaction mixture at normal pressure, that is, lower than the boiling point of a mixture of 4,4'-dichlorodiphenylsulfone and an alkali metal hydroxide in a mixed solvent. The boiling point of a mixed solvent with dimethyl sulfoxide/water weight ratio of 50150 is about 109°C, and the boiling point of a mixed solvent of 9515 is about 163°C.
A mixture of 4.4' dichlorodiphenyl sulfone and an alkali metal hydroxide in a mixed solvent initially boils at a temperature much higher than the boiling point of the mixed solvent, and then as the reaction progresses, the boiling temperature gradually decreases. It's coming.
反応温度が１４０℃未満の場合は、反応は極めてゆるや
かにしか進行しない。反応に要する時間は、混合溶媒の
組成、アルカリ金属水酸化物の使用量、および反応温度
によって異なるが、比較的短く、通常４〜ｌＯ時間であ
る。When the reaction temperature is less than 140°C, the reaction proceeds only very slowly. The time required for the reaction varies depending on the composition of the mixed solvent, the amount of alkali metal hydroxide used, and the reaction temperature, but is relatively short, usually 4 to 10 hours.
反応が終わったとき、反応混合物は、液中にアルカリ金
属塩化物が浮遊した状態になっている。When the reaction is completed, the reaction mixture is in a state in which the alkali metal chloride is suspended in the liquid.
４．４′−ジクロロジフェニルスルホンの加水分解によ
って生成した４、４′−ジヒドロキシジフェニルスルホ
ンは、アルカリ金属の塩となって液相中に溶解している
。4,4'-dihydroxydiphenylsulfone produced by hydrolysis of 4,4'-dichlorodiphenylsulfone is dissolved in the liquid phase as an alkali metal salt.
ここで、反応混合物に、あるいは、反応混合物を濾過し
てアルカリ金属塩化物を除去した溶液に水を加える。水
の量は、次の中和工程で生成するアルカリ金属の塩を溶
解するのに十分な量であることが好ましい。Here, water is added to the reaction mixture or to the solution from which the alkali metal chloride has been removed by filtering the reaction mixture. Preferably, the amount of water is sufficient to dissolve the alkali metal salt produced in the subsequent neutralization step.
４．４′−ジヒドロキシジフェニルスルホンのアルカリ
金属塩を溶解している溶液に酸を加えて中和し、４．４
′−ジヒドロキシジフェニルスルホンを析出せしめる。4. Add acid to a solution in which an alkali metal salt of 4'-dihydroxydiphenyl sulfone is dissolved to neutralize it.
'-dihydroxydiphenylsulfone is precipitated.
酸としてはどんなものを選んでもよいが、生成する塩の
水への溶解度が大きいものを選ぶことが好ましい。析出
した４、４′−ジヒドロキシジフェニルスルホンを濾別
し、水によって洗浄する。洗浄水中のアルカリ金属イオ
ン、塩素イオン、または中和に用いた酸に由来するアニ
オンの消滅によって、洗浄の完了を知ることができる。Any acid may be selected, but it is preferable to select one in which the resulting salt has a high solubility in water. The precipitated 4,4'-dihydroxydiphenylsulfone is filtered off and washed with water. Completion of cleaning can be determined by the disappearance of alkali metal ions, chloride ions, or anions derived from the acid used for neutralization in the cleaning water.
洗浄を終わった４、４′−ジヒドロキシジフェニルスル
ホンは乾燥される。After washing, the 4,4'-dihydroxydiphenylsulfone is dried.
本発明の方法においては、反応中における異性化が起こ
らず、生成したジクロロジフェニルスルホン中の４．４
′一体の含量は、原料に用いたジクロロジフェニルスル
ホン中の４・４’一体の含量と同じである。In the method of the present invention, isomerization does not occur during the reaction, and 4.4% of the dichlorodiphenyl sulfone produced is
The content of 4,4' is the same as the content of 4,4' in the dichlorodiphenyl sulfone used as the raw material.
以下に、実施例をあげて、本発明をさらに説明する。 The present invention will be further explained below with reference to Examples.
実施例 ｌ
温度計、還流冷却器、撹拌器をつけた５００−のステン
レス鋼製容器にジメチルスルホキシド８０ｇ１水２０ｇ
１純度９９．０％の４．４′−ジクロロジフェニルスル
ホン１００ｇ１、水酸化カリウム１３８ｇを仕込み、撹
拌しながら加熱した。温度が上昇すると４．４′−ジク
ロロジフェニルスルホンは溶解し、溶液が１８３℃に達
したとき沸騰が始まった。Example 1 80 g dimethyl sulfoxide 1 20 g water in a 500-mm stainless steel container equipped with a thermometer, reflux condenser, and stirrer.
1 100 g of 4,4'-dichlorodiphenylsulfone with a purity of 99.0% and 138 g of potassium hydroxide were charged and heated while stirring. As the temperature increased, the 4,4'-dichlorodiphenylsulfone dissolved and boiling began when the solution reached 183°C.
そのまま、加熱還流を続けると、液温は徐々に低下し、
４時間後には１４８℃になった。ここで、反応混合物を
冷却したのち水２００ｇを加えると、均一な透明液とな
った。さらに、水８００ｇで稀釈し、塩酸を徐々に加え
て酸性にした。析出した結晶を、濾過、水洗、乾燥して
、淡黄色の粉末８２．１ｇを得た。液体クロマトグラフ
ィーで分析すると、得られたこの４，４′−ジヒドロキ
シジフェニルスルホンの純度は９８．３％であった。If heating and refluxing is continued, the liquid temperature will gradually decrease.
After 4 hours, the temperature reached 148°C. Here, when 200 g of water was added after cooling the reaction mixture, it became a homogeneous transparent liquid. Furthermore, it was diluted with 800 g of water, and hydrochloric acid was gradually added to make it acidic. The precipitated crystals were filtered, washed with water, and dried to obtain 82.1 g of pale yellow powder. Analysis by liquid chromatography showed that the purity of the obtained 4,4'-dihydroxydiphenylsulfone was 98.3%.
実施例 ２
実施例１におけるジメチルスルホキシド、水、水酸化カ
リウムの量をそれぞれ５０ｇ 、５０ｇ 、１８４ｇに
変えて同様の操作を行ない、８３．２ ｇの淡黄色粉末
を得た。得られたこの４．４′−ジヒドロキシジフェニ
ルスルホンの純度は９９．１％であった。Example 2 The same operation as in Example 1 was carried out except that the amounts of dimethyl sulfoxide, water, and potassium hydroxide were changed to 50 g, 50 g, and 184 g, respectively, to obtain 83.2 g of pale yellow powder. The purity of the 4,4'-dihydroxydiphenylsulfone obtained was 99.1%.
比較例 １
実施例１における水酸化カリウムの量を８８ｇに変えて
、同様の操作を行ない、９０．０ ｇの淡黄色粉末を得
たが、この粉末は４．４′−ジヒドロキシジフェニルス
ルホン２１．３％、４−クロロ−４′−ヒドロキシジフ
エニルスルホン５１，３％ヲ含有シていた。Comparative Example 1 The same operation as in Example 1 was performed except that the amount of potassium hydroxide was changed to 88 g to obtain 90.0 g of pale yellow powder, which was 4.4'-dihydroxydiphenylsulfone 21. It contained 51.3% of 4-chloro-4'-hydroxydiphenyl sulfone.
比較例 ２
実施例２におけるジメチルスルホキシドと水の量を、そ
れぞれ２０ｇ、８０ｇに変えて同様の操作を行ない、８
２．７ ｇの淡黄色粉末を得た。この粉末は４．４’
−ジヒドロキシジフェニルスルホン２７．８％、４−ク
ロロ−４′−ヒドロキシジフェニルスルホン６５．６％
を含有していた。Comparative Example 2 The same operation as in Example 2 was carried out by changing the amounts of dimethyl sulfoxide and water to 20 g and 80 g, respectively.
2.7 g of pale yellow powder was obtained. This powder is 4.4'
-dihydroxydiphenylsulfone 27.8%, 4-chloro-4'-hydroxydiphenylsulfone 65.6%
It contained.
実施例 ３
ジメチルスルホキシド７０ｇ、水３０ｇ１純度９９、０
％の４．４’−ジクロロジフェニルスルホン１００ ｇ
、水酸化す） ＩＪウム１４０ｇを反応器に仕込み、
撹拌しながら、８時間加熱還流を行なった。Example 3 70 g of dimethyl sulfoxide, 30 g of water 1 purity 99.0
% 4.4'-dichlorodiphenylsulfone 100 g
, hydroxide) 140g of IJium was charged into the reactor,
The mixture was heated under reflux for 8 hours while stirring.
反応混合物を冷却したのち、析出している塩化ナトリウ
ムを濾別した。濾液に水１０００ｇを加えて希釈したの
ち、塩酸を加えて徐々に酸性にした。析出した結晶を、
濾過、水洗、乾燥して、淡黄色の粉末８４．８ ｇを得
た。得られたこの４，４′−ジヒドロキシジフェニルス
ルホンの純度は９８．７％であった。After cooling the reaction mixture, precipitated sodium chloride was filtered off. The filtrate was diluted by adding 1000 g of water, and then hydrochloric acid was added to gradually make it acidic. The precipitated crystals are
It was filtered, washed with water, and dried to obtain 84.8 g of pale yellow powder. The purity of the 4,4'-dihydroxydiphenylsulfone obtained was 98.7%.
本発明の方法によれば、工業的に容易に人手し得る、純
度の高い４．４′−ジクロロジフェニルスルホンから、
−段の反応で、高純度の４．４′−ジヒドロキシジフェ
ニルスルホンを製造することができる。反応は、常圧で
進行するので、特殊な加圧容器などを必要とせず、また
反応時間が比較的短いので、有利に実施し得る。According to the method of the present invention, from highly pure 4,4'-dichlorodiphenyl sulfone, which can be easily produced manually,
High purity 4,4'-dihydroxydiphenyl sulfone can be produced by the -stage reaction. Since the reaction proceeds at normal pressure, no special pressurized container is required, and the reaction time is relatively short, so it can be carried out advantageously.
Claims (1)
ルスルホキシド／水の重量比が５０／５０以上９５／５
未満であるジメチルスルホキシド／水混合溶媒中におい
て、４，４′−ジクロロジフェニルスルホン１モル当り
５モル以上１５モル未満の水酸化リチウム、水酸化ナト
リウムおよび水酸化カリウムよりなる群より選ばれた１
種以上の化合物を加えて加水分解することを特徴とする
、４，４′−ジヒドロキシジフェニルスルホンの製造方
法。1,4,4'-dichlorodiphenyl sulfone in a dimethyl sulfoxide/water weight ratio of 50/50 or more 95/5
1 selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide in an amount of 5 mol or more and less than 15 mol per 1 mol of 4,4'-dichlorodiphenyl sulfone in a dimethyl sulfoxide/water mixed solvent that is less than
1. A method for producing 4,4'-dihydroxydiphenyl sulfone, which comprises adding and hydrolyzing more than one type of compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1069162A JP2758016B2 (en) | 1989-03-23 | 1989-03-23 | Method for producing 4,4'-dihydroxydiphenyl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1069162A JP2758016B2 (en) | 1989-03-23 | 1989-03-23 | Method for producing 4,4'-dihydroxydiphenyl sulfone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02250861A true JPH02250861A (en) | 1990-10-08 |
| JP2758016B2 JP2758016B2 (en) | 1998-05-25 |
Family
ID=13394732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1069162A Expired - Fee Related JP2758016B2 (en) | 1989-03-23 | 1989-03-23 | Method for producing 4,4'-dihydroxydiphenyl sulfone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2758016B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS501020A (en) * | 1973-05-08 | 1975-01-08 | ||
| JPS62167732A (en) * | 1986-01-20 | 1987-07-24 | Asahi Chem Ind Co Ltd | Hydrolysis of aromatic iodide |
-
1989
- 1989-03-23 JP JP1069162A patent/JP2758016B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS501020A (en) * | 1973-05-08 | 1975-01-08 | ||
| JPS62167732A (en) * | 1986-01-20 | 1987-07-24 | Asahi Chem Ind Co Ltd | Hydrolysis of aromatic iodide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2758016B2 (en) | 1998-05-25 |
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