JPH0269454A - Production of 4-(phenylthio)benzenesulfonic acid - Google Patents
Production of 4-(phenylthio)benzenesulfonic acidInfo
- Publication number
- JPH0269454A JPH0269454A JP22106788A JP22106788A JPH0269454A JP H0269454 A JPH0269454 A JP H0269454A JP 22106788 A JP22106788 A JP 22106788A JP 22106788 A JP22106788 A JP 22106788A JP H0269454 A JPH0269454 A JP H0269454A
- Authority
- JP
- Japan
- Prior art keywords
- diphenyl sulfide
- phenylthio
- acid
- chlorinated hydrocarbon
- hydrocarbon solvent
- 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.)
- Pending
Links
- GLEUKHIEIHXBQO-UHFFFAOYSA-N 4-phenylsulfanylbenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1SC1=CC=CC=C1 GLEUKHIEIHXBQO-UHFFFAOYSA-N 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims abstract description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- -1 aromatic sulfonic acids Chemical class 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- YLFAXWUBPTYCHC-UHFFFAOYSA-N 2-phenylsulfanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1SC1=CC=CC=C1 YLFAXWUBPTYCHC-UHFFFAOYSA-N 0.000 description 1
- MSSOQDMBUKCNTK-UHFFFAOYSA-N 4-(4-sulfophenyl)sulfanylbenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1SC1=CC=C(S(O)(=O)=O)C=C1 MSSOQDMBUKCNTK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000277269 Oncorhynchus masou Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 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
- 239000000575 pesticide Substances 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、−数式（Ｉ）で表わされる４−（フェニルチ
オ）ベンゼンスルホン酸の製法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing 4-(phenylthio)benzenesulfonic acid represented by formula (I).
４−（フェニルチオ）ベンゼンスルホン酸は比較的新し
い化合物（ケミカルアブストラクト・レジストＮ ｏ
、 ９５６８４−３９−２）であって、従来、難燃化剤
（米国特許出願Ｎ ｏ 、 ６２６９３３．７３３０１
５．７３３０１７）としての用途が開示されている。4-(Phenylthio)benzenesulfonic acid is a relatively new compound (Chemical Abstract Resist No.
, 95684-39-2) and conventionally flame retardants (U.S. Patent Application No. 626933.73301).
5.733017) is disclosed.
しかしながら、近年この化合物は、医薬、農薬。However, in recent years this compound has been used in medicines and pesticides.
機能性材料合成等のための重要な合成中間体として、広
くその有用性が認められつつある。４−（フェニルチオ
）ベンゼンスルホン酸は、それ自体でも有用であるが、
スルホニルクロリドやチオールに導くことが可能で、そ
の結果、種々の化合物合成の出発物質となり得る。さら
に２つのフェニル基にはさまれた２価硫黄部分を酸化し
て、その酸化数を変化させることにより、巾広い用途が
期待できる。Its usefulness is being widely recognized as an important synthetic intermediate for the synthesis of functional materials. 4-(Phenylthio)benzenesulfonic acid is useful on its own, but
It can lead to sulfonyl chlorides and thiols, and as a result, it can serve as a starting material for the synthesis of various compounds. Furthermore, by oxidizing the divalent sulfur moiety sandwiched between two phenyl groups and changing its oxidation number, a wide range of applications can be expected.
従来の技術
この化合物は前述のように有用であるにもかかわらず、
その使用範囲は今まで主に難燃化剤に限定されてきた。Prior Art Despite the usefulness of this compound as mentioned above,
Until now, their scope of use has been mainly limited to flame retardants.
この原因の１つとして、この化合物の工業的製法が未だ
確立されておらず、安価に大量に、供給され得なかった
ことが考えられる。One possible reason for this is that an industrial manufacturing method for this compound has not yet been established, and it has not been possible to supply it in large quantities at low cost.
４−（フェニルチオ）ベンゼンスルホン酸のバリウム塩
の存在は古くより知られていた（Ｂｅ ｒ、、 ２
６． ９９３ （１８９３））。The existence of barium salt of 4-(phenylthio)benzenesulfonic acid has been known for a long time (Ber, 2
6. 993 (1893)).
しかしながらこの時点においてはスルホン酸の置換位置
がわかっておらず、しかも遊離酸の形で単離することは
できなかった。However, at this point, the substitution position of the sulfonic acid was not known, and it was not possible to isolate it in the form of the free acid.
４位にスルホン酸基が入っていることは１９５６年にバ
リウム塩のＩＲをはかることにより始めて明らかとなっ
たが（Ｊ、 Ｃｈｅｍ。The presence of a sulfonic acid group at the 4-position was first revealed in 1956 by IR measurements of barium salts (J, Chem.
Ｓｏｃ、、 ３２４６ （１９５６）） 、この時
点においても４−（フェニルチオ）ベンゼンスルホン酸
を遊離酸の形で得ることはできなかった。Soc., 3246 (1956)), 4-(phenylthio)benzenesulfonic acid could not be obtained in the form of free acid at this time either.
上記スルホン酸塩は、それ自身が種々の化合物合成の出
発物質となり得る。しかし、スルホン酸塩は一般に水溶
液から取り出されるため、乾燥に時間を要したり、塩化
チオニル等を用いて酸クロリドとするときには、系内に
塩が生ずる等の問題点があった。従って４−（フェニル
チオ）ベンゼンスルホン酸を遊離酸の形で得ることは前
記の塩の形で得るよりも工業的に有用と考えられる。The sulfonate itself can serve as a starting material for the synthesis of various compounds. However, since sulfonate salts are generally extracted from an aqueous solution, there are problems such as it takes a long time to dry, and when thionyl chloride or the like is used to form an acid chloride, salts are formed in the system. Therefore, obtaining 4-(phenylthio)benzenesulfonic acid in the form of the free acid is considered to be industrially more useful than obtaining it in the form of the salt.
今までこの化合物が遊離酸の形でほとんど取り出された
ことがないのは、一般に芳香族スルホン酸は無水の状態
では熱安定性が低いためである。The reason why this compound has rarely been extracted in the form of a free acid is that aromatic sulfonic acids generally have low thermal stability in an anhydrous state.
（Ｓｙｎｔｈｅｓｉｓ、 １（１９６９）。(Synthesis, 1 (1969).
Ｊ、 Ｏｒｇ、 Ｃｈｅｍ、、 ３５゜合
成法の１例として、液体二酸化硫黄を反応溶媒として用
い、ジフェニルスルフィドを三酸化硫黄でスルホン化す
る方法があるが、（Ｇａｚｚ。J, Org, Chem, 35° As an example of a synthetic method, there is a method in which diphenyl sulfide is sulfonated with sulfur trioxide using liquid sulfur dioxide as a reaction solvent (Gazz.
Ｃｈｉｍ、 Ｉｔａｌ、 １１４． ５４３（
１９８４））この方法は、かなり実用性に乏しい。とい
うのは、溶媒として用いる二酸化硫黄の沸点は一１０℃
と低く、また三酸化硫黄は、その激しい化学反応性の故
に取り扱いが難しいためである。生成物の粗収率は９６
％と高いが、その精製にはかなりの工程を要し、収率は
不明であるが融点８１〜８３℃の結晶を得ている。従っ
てこの方法は工業的に実施可能な方法とはなり得なかっ
た。Chim, Ital, 114. 543(
(1984)) This method is quite impractical. This is because the boiling point of sulfur dioxide used as a solvent is -10°C.
This is because sulfur trioxide is difficult to handle due to its intense chemical reactivity. The crude yield of product is 96
%, but its purification requires a considerable number of steps, and although the yield is unknown, crystals with a melting point of 81 to 83°C have been obtained. Therefore, this method could not be an industrially viable method.
発明が解決しようとする問題点
以上示してきたように、従来の方法はスルホン化剤９反
応溶媒共に工業化という見地から見ると、それぞれ大き
な問題点を有していた。そこで本発明者らは４−（フェ
ニルチオ）ベンゼンスルホン酸を製造するに際し、安価
な原料であるジフェニルスルフィドをスルホン化する方
法について鋭意検討し、工業的に実施可能な製法を確立
するべく努力した。この際、ジフェニルスルフィドは当
然ｏ−，ｐ−配向性であるので、Ｐ−異性体のみを収率
よく得ることも考慮する必要があった。Problems to be Solved by the Invention As shown above, the conventional methods, both the sulfonating agent and the reaction solvent, have had major problems from the standpoint of industrialization. Therefore, when producing 4-(phenylthio)benzenesulfonic acid, the present inventors conducted intensive studies on a method of sulfonating diphenyl sulfide, which is an inexpensive raw material, and made efforts to establish an industrially practicable production method. At this time, since diphenyl sulfide naturally has o- and p-orientation, it was also necessary to consider obtaining only the P-isomer in good yield.
問題点を解決するための手段
本発明の方法により４−（フェニルチオ）ベンゼンスル
ホン酸を製造するに際し、留意すべき点は次の２点であ
った。まず、フェニルチオ基を持つフェニル環はＯ−、
Ｐ−配向性を有するためにＰ−異性体のみを選択率よ（
得ること、つぎにジフェニルスルフィドは硫黄原子をは
さんで）工ニル環を２個有するので、両フェニル環にス
ルホン酸基の導入された化合物を作らないことであった
。Means for Solving the Problems When producing 4-(phenylthio)benzenesulfonic acid by the method of the present invention, the following two points should be kept in mind. First, a phenyl ring with a phenylthio group is O-,
Since it has P-orientation, the selectivity for only P-isomer (
Next, since diphenyl sulfide has two engineered nyl rings (with a sulfur atom in between), it was important not to create a compound in which sulfonic acid groups were introduced into both phenyl rings.
従来、ジフェニルスルフィドのスルホン化としては先に
挙げた三酸化硫黄を用いる方法が知られているが、上記
２つの条件を満足し、かつ工業的に利用可能なスルホン
化剤について鋭意検討を加えたところ、クロロ硫酸がこ
の用途に好適であることを見い出した。Conventionally, the method using sulfur trioxide mentioned above has been known for sulfonation of diphenyl sulfide, but we have conducted extensive research on a sulfonating agent that satisfies the above two conditions and is industrially usable. However, it has been discovered that chlorosulfuric acid is suitable for this purpose.
即ちクロロ硫酸をスルホン化剤とするときには、ジフェ
ニルスルフィド自身が液体であるので、反応溶媒を用い
なくても、単に後者中に前者を滴下、撹拌するだけで反
応は進行する。しかし生成物である４−（フェニルチオ
）ベンゼンスルホン酸が固体として、系内に析出してく
るため、反応を完結させることは困難で溶媒の使用が必
要となる。That is, when chlorosulfuric acid is used as the sulfonating agent, since diphenyl sulfide itself is a liquid, the reaction proceeds simply by dropping the former into the latter and stirring, without using a reaction solvent. However, the product 4-(phenylthio)benzenesulfonic acid precipitates in the system as a solid, making it difficult to complete the reaction and requiring the use of a solvent.
そこで本発明者らは、溶媒について種々検討した結果、
塩素化炭化水素溶媒が最も好い結果を与えることを見出
した。塩素化炭化水素溶媒としては、クロロ硫酸き反応
せず、ジフェニルスルフィドを溶解させるものであれば
、特に制限されるものではないが、就中、ジクロロエタ
ン、クロロホルム、ジクロロメタン、テトラクロロエタ
ン、クロロベンゼン等を用いれば好収率で目的物が得ら
れる。これらの溶媒は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。Therefore, as a result of various studies regarding solvents, the present inventors found that
We have found that chlorinated hydrocarbon solvents give the best results. The chlorinated hydrocarbon solvent is not particularly limited as long as it does not react with chlorosulfuric acid and dissolves diphenyl sulfide, but among others, dichloroethane, chloroform, dichloromethane, tetrachloroethane, chlorobenzene, etc. can be used. The desired product can be obtained in good yield. These solvents may be used alone or in combination of two or more.
上記溶媒中で反応を行なった場合、通常９０％以上の反
応収率が得られる。反応液よりの生成物の取り出しも非
常に簡単で、反応中に析出してきた生成物を単に炉取す
るだけで良い場合が多い。When the reaction is carried out in the above solvent, a reaction yield of 90% or more is usually obtained. It is also very easy to remove the product from the reaction solution, and in many cases it is sufficient to simply remove the product that has precipitated during the reaction.
反応に低沸点の溶媒、たとえばジクロロエタン等を用い
た場合には、得られた結晶の乾燥も低い温度でよく、４
−（フェニルチオ）ベンゼンスルホン酸を、熱変性させ
ることなく純度よく得ることができる。生成物中には副
生成物の２−（フェニルチオ）ベンゼンスルホン酸は見
い出されず、反応か位置選択的に進んでいることが確認
できた。When a low boiling point solvent such as dichloroethane is used in the reaction, the resulting crystals may be dried at a low temperature;
-(Phenylthio)benzenesulfonic acid can be obtained with high purity without thermal denaturation. The by-product 2-(phenylthio)benzenesulfonic acid was not found in the product, confirming that the reaction proceeded regioselectively.
本反応は反応温度−１０’Ｃ〜５０℃で行なうことが好
ましい。反応温度が５０°Ｃより高いと両フェニル基の
４，４′位にスルホン基の導入された副生成物が増加し
、また−１０℃より低いと反応速度が遅くなり経済的に
不利となる。This reaction is preferably carried out at a reaction temperature of -10'C to 50C. If the reaction temperature is higher than 50°C, by-products with sulfone groups introduced at the 4 and 4' positions of both phenyl groups will increase, and if it is lower than -10°C, the reaction rate will be slow, which is economically disadvantageous. .
ジフェニルスルフィドに対するクロロ硫酸の使用量は、
モル比で０．６〜１．２．好ましくは０．８〜１．２で
ある。０．６よりも少ないと、未反応のジフェニルスル
フィドの回収に手間がかかり、１．２よりも大きいと両
方のフェニル基の４．４′位がスルホン化されたジスル
ホン酸が生成する。The amount of chlorosulfuric acid used for diphenyl sulfide is
molar ratio of 0.6 to 1.2. Preferably it is 0.8-1.2. When it is less than 0.6, it takes time to recover unreacted diphenyl sulfide, and when it is more than 1.2, a disulfonic acid in which the 4.4' positions of both phenyl groups are sulfonated is produced.
実施例
以下に実施例を挙げて本発明の方法を具体的に説明する
。EXAMPLES The method of the present invention will be specifically explained with reference to Examples below.
生成物の定量法
生成物の定量は液体クロマトグラフィー（Ｌ Ｃ）を用
いて行なった。条件は以下の通りである。Quantification of the product Quantification of the product was performed using liquid chromatography (LC). The conditions are as follows.
機種 品性 ＬＣ−６Ａ
カラム ＭＭＣ−ＯＤＳ （Ａ−３１２）６φＸ１５０
ｍｍ
移動相 メタノール：水 ７：３ １ｍｌ／ｍｉｎオー
ブン温度 ５０°Ｃ
保持時間
４−（フェニルチオ）ペンセンスルホン酸３．６分
４．４−−チオジベンゼンスルホン酸 ２．７分実施例
１
撹拌棒、温度計を備えた１１４つロフラスコにジフェニ
ルスルフィド１８６ｇ （１ｍｏｌ）とジクロロエタン
７５０ｇをあらかじめ仕込み、温度をＯｏＣとした。そ
こへクロロ硫酸１１６．５ ｇ （１ｍｏ ｌ）を反応
温度を０℃に保ちながら３時間を要して滴下した。同温
度で２時間撹拌後析出した結晶を炉取し、乾燥すると純
度９９％の４−（フェニルチオ）ベンゼンスルホン酸２
１６ｇ （対ジフェニルスルフィド収率８１％）得られ
た。炉液には３９ｇ（対ジフェニルスルフィド収率１５
％）の４−（フェニルチオ）ベンゼンスルホン酸が含ま
れていた。両収率を合計して反応収率（９６％）また前
者の収率（８１％）を以て取得収率とした。Model Quality LC-6A Column MMC-ODS (A-312) 6φX150
mm Mobile phase Methanol:water 7:3 1ml/min Oven temperature 50°C Retention time 4-(phenylthio)pensenesulfonic acid 3.6 minutes 4.4-thiodibenzenesulfonic acid 2.7 minutes Example 1 Stirring 186 g (1 mol) of diphenyl sulfide and 750 g of dichloroethane were charged in advance into a 114-bottle flask equipped with a rod and a thermometer, and the temperature was set at OoC. Thereto, 116.5 g (1 mol) of chlorosulfuric acid was added dropwise over 3 hours while maintaining the reaction temperature at 0°C. After stirring at the same temperature for 2 hours, the precipitated crystals were collected in a furnace and dried to give 4-(phenylthio)benzenesulfonic acid 2 with a purity of 99%.
16 g (81% yield based on diphenyl sulfide) was obtained. The furnace solution contained 39 g (yield of diphenyl sulfide: 15
%) of 4-(phenylthio)benzenesulfonic acid. The reaction yield (96%) was obtained by adding up both yields, and the former yield (81%) was used as the obtained yield.
得られた結晶の融点は８７〜８８°Ｃ９１Ｈ−ＮＭＲ，
Ｃ−ＮＭＲ分析値は文献値（Ｇａｚｚ、 Ｃｈｉｍ
、 Ｉｔａｌ、。The melting point of the obtained crystal was 87-88°C91H-NMR,
C-NMR analysis values are the literature values (Gazz, Chim
, Ital,.
１１４、 ５４３（１９８４））と一致した。結晶中
に４．４′−チオジベンゼンスルホン酸は認められなか
った。114, 543 (1984)). No 4,4'-thiodibenzenesulfonic acid was observed in the crystals.
実施例２〜４
反応に用いる溶媒の種類を変化させた以外は実施例１と
同様に反応を行ない、表の結果を得た。Examples 2 to 4 The reaction was carried out in the same manner as in Example 1, except that the type of solvent used in the reaction was changed, and the results shown in the table were obtained.
表
発明の効果
本発明により、従来は合成が困難とされていた４−（フ
ェニルチオ）ベンゼンスルホン酸を容易に合成すること
が可能となった。即ち、工業的に安価なりロロ硫酸をス
ルホン化剤として、塩素化炭化水素溶媒中でジフェニル
スルフィドをスルホン化することにより、選択率よく、
４−（フェニルチオ）ベンゼンスルホン酸を得ることが
できる。Effects of the Invention The present invention has made it possible to easily synthesize 4-(phenylthio)benzenesulfonic acid, which was conventionally considered difficult to synthesize. That is, by sulfonating diphenyl sulfide in a chlorinated hydrocarbon solvent using industrially inexpensive lolo-sulfuric acid as a sulfonating agent, it is possible to sulfonate diphenyl sulfide with high selectivity.
4-(phenylthio)benzenesulfonic acid can be obtained.
溶媒はごく一般的な塩素化炭化水素溶媒が使用可能であ
り、生成物は反応中に結晶として得られるので、濾過の
みで生成物を収率よく得ることができる。低沸点の溶媒
を選ぶと製品の乾燥も容易で、経済的にもより有利に、
本発明の方法を実施することができる。As the solvent, a very common chlorinated hydrocarbon solvent can be used, and since the product is obtained as crystals during the reaction, the product can be obtained in good yield simply by filtration. Choosing a solvent with a low boiling point makes it easier to dry the product and is more economically advantageous.
The method of the invention can be practiced.
出願人 製鉄化学工業株式会社 代表者 増 １）裕 治Applicant: Steel Chemical Industry Co., Ltd. Representative Masu 1) Yuji
Claims (3)
水素溶媒中で反応させることを特徴とする４−（フェニ
ルチオ）ベンゼンスルホン酸の製法。(1) A method for producing 4-(phenylthio)benzenesulfonic acid, which comprises reacting diphenylsulfide and chlorosulfuric acid in a chlorinated hydrocarbon solvent.
ルム、ジクロロメタン、クロロベンゼンよりなる群から
選ばれた少なくとも一種である特許請求の範囲（１）記
載の方法。(2) The method according to claim (1), wherein the chlorinated hydrocarbon solvent is at least one selected from the group consisting of dichloroethane, chloroform, dichloromethane, and chlorobenzene.
比が０．６〜１．２、反応温度−１０℃〜５０℃で反応
を行なう特許請求の範囲（１）記載の方法。(3) The method according to claim (1), wherein the molar ratio of chlorosulfuric acid to diphenyl sulfide is 0.6 to 1.2 and the reaction temperature is -10°C to 50°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22106788A JPH0269454A (en) | 1988-09-02 | 1988-09-02 | Production of 4-(phenylthio)benzenesulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22106788A JPH0269454A (en) | 1988-09-02 | 1988-09-02 | Production of 4-(phenylthio)benzenesulfonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0269454A true JPH0269454A (en) | 1990-03-08 |
Family
ID=16760974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22106788A Pending JPH0269454A (en) | 1988-09-02 | 1988-09-02 | Production of 4-(phenylthio)benzenesulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0269454A (en) |
-
1988
- 1988-09-02 JP JP22106788A patent/JPH0269454A/en active Pending
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