JPH0425946B2 - - Google Patents
Info
- Publication number
- JPH0425946B2 JPH0425946B2 JP60049165A JP4916585A JPH0425946B2 JP H0425946 B2 JPH0425946 B2 JP H0425946B2 JP 60049165 A JP60049165 A JP 60049165A JP 4916585 A JP4916585 A JP 4916585A JP H0425946 B2 JPH0425946 B2 JP H0425946B2
- Authority
- JP
- Japan
- Prior art keywords
- thiophenol
- methanesulfonyloxy
- polythiobisphenol
- reaction
- 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.)
- Expired - Lifetime
Links
- IFIKILAPWJGSPO-UHFFFAOYSA-N (4-sulfanylphenyl) methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=C(S)C=C1 IFIKILAPWJGSPO-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000003328 mesylation reaction Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 methanesulfonyloxyphenylthioacetate Chemical compound 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 description 4
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VQVBDNNSGNHKGS-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)trisulfanyl]phenol Chemical compound OC1=CC=CC=C1SSSC1=CC=CC=C1O VQVBDNNSGNHKGS-UHFFFAOYSA-N 0.000 description 2
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WXVUCMFEGJUVTN-UHFFFAOYSA-N phenyl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC=C1 WXVUCMFEGJUVTN-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FNXXLDHPVGHXEM-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)disulfanyl]phenol Chemical compound OC1=CC=CC=C1SSC1=CC=CC=C1O FNXXLDHPVGHXEM-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 230000006191 S-acylation Effects 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005947 deacylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
［発明の目的］
本発明はポリチオビスフエノールをメシル化し
た後、還元することにより４−（メタンスルホニ
ルオキシ）チオフエノールを製造する方法を提供
することを目的とする。[Detailed Description of the Invention] [Object of the Invention] The object of the present invention is to provide a method for producing 4-(methanesulfonyloxy)thiophenol by mesylating polythiobisphenol and then reducing it. .
（産業上の利用分野）
４−（メタンスルホニオキシ）チオフエノール
は、カーバイト系又はリン酸系農薬の原料中間体
として有用な化合物である。(Industrial Application Field) 4-(methanesulfonioxy)thiophenol is a compound useful as a raw material intermediate for carbide-based or phosphoric acid-based pesticides.
（従来の技術）
これまでの文献、特許には、４−メルカプトフ
エノールから４−（メタンスルホニルオキシ）チ
オフエノールを合成する方法が知られている。例
えばボードウエルら［F.G.Bardwell＆P.
Bouten；J.Am.Chem.Soc.78．854（1956）］は、
４−メルカプトフエノールからＳ−アセチル−４
−メルカプトフエノールの合成について報告して
いる。特開昭54−5951には、Ｓ−アセチル−４−
メルカプトフエノールからメタンスルホニルオキ
シフエニルチオアセテートを経由して、４−（メ
タンスルホニルオキシ）チオフエノールを合成す
る方法が開示されている。すなわち
しかしながら４−（メタンスルホニルオキシ）
チオフエノールを工業的に製造する簡単で経済的
な方法な未だ知られていない。(Prior Art) A method for synthesizing 4-(methanesulfonyloxy)thiophenol from 4-mercaptophenol is known in literature and patents so far. For example, Bordwell et al. [FGBardwell & P.
Bouten; J.Am.Chem.Soc.78.854 (1956)]
4-mercaptophenol to S-acetyl-4
- Reports on the synthesis of mercaptophenol. In JP-A-54-5951, S-acetyl-4-
A method for synthesizing 4-(methanesulfonyloxy)thiophenol from mercaptophenol via methanesulfonyloxyphenylthioacetate is disclosed. i.e. However, 4-(methanesulfonyloxy)
There is still no known simple and economical method for industrially producing thiophenol.
（発明が解決しようとする問題点）
前記したように従来技術では、４−メルカプト
フエノールをメシル化する前後にＳ−アシル化、
脱アシル化反応が必要である。そのためSH基を
保護しなければならず、従つて余分の薬品代を要
し不経済であり、かつ工程が長くなり、収率も30
％程度低いことなど、工業的に決して有利な方法
ではない。(Problems to be Solved by the Invention) As mentioned above, in the prior art, S-acylation and
A deacylation reaction is required. Therefore, the SH group must be protected, which is uneconomical due to the extra cost of chemicals, and the process is lengthened, with a yield of 30%.
It is not an industrially advantageous method, as it is about a low %.
［発明の構成］
このような従来技術の欠点を改善し、４−（メ
タンスルホニルオキシ）チオフエノールを製造す
る方法について本発明者らは、鋭意検討を重ねた
結果、フエノールと一塩化硫黄とから一段階で合
成することが可能なポリチオビスフエノールを直
接メタンスルホニルクロリドでメシル化した後、
還元することにより４−（メタンスルホニルオキ
シ）チオフエノールを好収率で製造し得ることを
見出し本発明に到達した。さらに、反応条件、精
製造などについても検討を重ね、本発明を完成す
るに至つた。本発明の製法の反応過程を示せば次
の通りである。[Structure of the Invention] As a result of extensive research into a method for producing 4-(methanesulfonyloxy)thiophenol by improving the drawbacks of the prior art, the present inventors have developed a method for producing 4-(methanesulfonyloxy)thiophenol from phenol and sulfur monochloride. After direct mesylation of polythiobisphenol, which can be synthesized in one step, with methanesulfonyl chloride,
The present invention was achieved by discovering that 4-(methanesulfonyloxy)thiophenol can be produced in good yield by reduction. Furthermore, the present invention was completed after repeated studies on reaction conditions, purification, etc. The reaction process of the production method of the present invention is as follows.
（問題点を解決するための手段）
本発明の要旨はポリチオビスフエノールをメタ
ンスルホニルクロリドでメシル化した後に還元し
て４−（メタンスルホニルオキシ）チオフエノー
ルに変換することを特徴とする４−（メタンスル
ホニルオキシ）チオフエノールの製法である。 (Means for Solving the Problems) The gist of the present invention is that polythiobisphenol is mesylated with methanesulfonyl chloride and then reduced to convert it into 4-(methanesulfonyloxy)thiophenol. This is a method for producing (methanesulfonyloxy)thiophenol.
本発明において、ポリチオビスフエノールとし
てはジオビスフエノール、トリチオビスフエノー
ル、又はそれらの混合物のいずれでもよく、フエ
ノールと一塩化硫黄とから一段階で容易に合成す
ることができる。フエノールを出発物質とした場
合、従来の方法では４−メルカプトフエノールを
得るには、通常２工程が必要であり、４−（メタ
ンスルホニルオキシ）チオフエノールに至るまで
には前記のようにさらに３工程を要し、通算５工
程を必要とする。本発明の方法によれば、フエノ
ールを出発物質とした場合に、ポリチオビスフエ
ノールは１工程で生成し、４−（メタンスルホニ
ルオキシ）チオフエノールを製造するにはさらに
２工程を要するのみで、通算３工程であることか
ら、従来の４−メルカプトフエノールを経由する
方法に比較して大幅な工程短縮となる。 In the present invention, the polythiobisphenol may be diobisphenol, trithiobisphenol, or a mixture thereof, and can be easily synthesized in one step from phenol and sulfur monochloride. When using phenol as a starting material, conventional methods usually require two steps to obtain 4-mercaptophenol, and three additional steps as described above to obtain 4-(methanesulfonyloxy)thiophenol. This requires a total of 5 steps. According to the method of the present invention, when phenol is used as a starting material, polythiobisphenol is produced in one step, and only two additional steps are required to produce 4-(methanesulfonyloxy)thiophenol. Since there are three steps in total, the steps are significantly shortened compared to the conventional method using 4-mercaptophenol.
また、ポリチオビスフエノール中には、通常不
純物として、モノスルフイドが含まれているが、
モノスルフイドのメシル化体ほ、チオール基のア
ルカリ抽出法から、容易に分離することができ
る。さらに、後述のように、本発明の方法は総合
収率が60％となり、これは従来法がたかだか30％
程度であつたこと考慮すれば、はるかにすぐれた
有利な方法である。 In addition, polythiobisphenol usually contains monosulfide as an impurity, but
Mesylated monosulfides can be easily separated using the alkaline extraction method of thiol groups. Furthermore, as will be described later, the method of the present invention has an overall yield of 60%, which is 30% at most in the conventional method.
Considering that it was only a matter of time, this is a much better and more advantageous method.
本発明において、メシル化反応の触媒としては
トリエチルアミン等の第３級アミン、ピリジン等
の含窒素芳香族化合物、または、NaOH，
K2CO3等の無機塩基が適当であり、溶媒として
は酢酸エチル等のエステル類、アセトニトリル等
のニトリル類、またはジオキサン等のエーテル類
が一般に使用可能である。反応温度は、０〜10℃
の比較的低温が好適であり、低すぎると応応が進
行せず、また高すぎると副反応をおこす可能性が
あり収率が低下する。反応の圧力は、常圧、加圧
のいずれでも実施できるが、安全性、経済性から
考えて常圧の方が好ましい。反応のモル比は理論
量通りで良くまたこれが最適である。メシル化剤
のモル比が小さい場合にはメシル化が不安全であ
り、モル比が大きい場合には、過剰分のメシル化
剤が反応液に残るため分離が必要となり不経済で
ある。 In the present invention, as a catalyst for the mesylation reaction, a tertiary amine such as triethylamine, a nitrogen-containing aromatic compound such as pyridine, or NaOH,
Inorganic bases such as K 2 CO 3 are suitable, and esters such as ethyl acetate, nitrites such as acetonitrile, or ethers such as dioxane can generally be used as solvents. Reaction temperature is 0~10℃
A relatively low temperature is preferable; if it is too low, the reaction will not proceed, and if it is too high, side reactions may occur and the yield will decrease. The reaction can be carried out at either normal pressure or elevated pressure, but normal pressure is preferable from the viewpoint of safety and economy. The molar ratio of the reaction may be the same as the theoretical amount, and this is optimal. If the molar ratio of the mesylating agent is small, mesylation is unsafe, and if the molar ratio is large, an excess of the mesylating agent remains in the reaction solution, making separation necessary and uneconomical.
（作用）
本発明の反応は、原料としてポリチオビスフエ
ノールを用いることによりフエノール性OH基に
対するメシル化が選択的に、かつ、ほぼ定量的に
進行する。これに反し、４−（メタンスルホニル
オキシ）チオフエノールを原料とした場合には、
フエノール性OH基よりもSHの方がメタンスル
ホニルクロリドとの反応性が高いため、SH基を
アシル化して保護した後メシル化し、その後脱ア
シル化する必要がある。ジチオビスフエノールを
メシル化後、還元した場合には４−（メタンスル
ホニルオキシ）チオフエノールのみが生成する
が、トリチオビスフエノールをメシル化後、還元
した場合には、４−（メタンスルホニルオキシ）
チオフエノールと硫化水素が生成するので、式(1)
におけるｎが２、または３の場合、もしくはこれ
らが混合している場合にもそのまま反応して目的
物を得ることができる。(Function) In the reaction of the present invention, mesylation of phenolic OH groups proceeds selectively and almost quantitatively by using polythiobisphenol as a raw material. On the other hand, when 4-(methanesulfonyloxy)thiophenol is used as the raw material,
Since SH has higher reactivity with methanesulfonyl chloride than the phenolic OH group, it is necessary to acylate and protect the SH group, then mesylate it, and then deacylate it. When dithiobisphenol is mesylated and then reduced, only 4-(methanesulfonyloxy)thiophenol is produced, but when trithiobisphenol is mesylated and then reduced, 4-(methanesulfonyloxy) is produced.
Thiophenol and hydrogen sulfide are generated, so Equation (1)
Even when n is 2 or 3, or when these are mixed, the desired product can be obtained by reacting as is.
［実施例］
以下実施例を示して本発明をさらに詳細に説明
する。ここで本発明者らは、亜鉛／酸による還元
方法を用いたが、これのみに限定されることな
く、従来からよく知られているLiAlH4、NaBH4
などの金属水素化物を用いる方法、トリフエニル
ホスフインを用いる方法なども還元方法として用
いることができる。以下特記しないかぎり、部は
重量部である。[Example] The present invention will be explained in more detail by referring to Examples below. Here, the present inventors used a reduction method using zinc/acid, but the method is not limited to this, and the well-known methods such as LiAlH 4 and NaBH 4
A method using a metal hydride such as, a method using triphenylphosphine, etc. can also be used as a reduction method. Unless otherwise specified below, parts are by weight.
実施例 １
ポリチオビスフエノール
フエノール94.1ｇ（１モル）をＮ，Ｎ−ジメチ
ルホルムアミド380ｇに溶解し、−20℃に冷却す
る。一塩化硫黄67.5ｇ（0.5モル）をトルエン130
ｇに溶解し、−20〜15℃に保つたフエノール溶液
に１時間で滴下する。Example 1 Polythiobisphenol 94.1 g (1 mol) of phenol is dissolved in 380 g of N,N-dimethylformamide and cooled to -20°C. 67.5 g (0.5 mol) of sulfur monochloride to 130 g of toluene
g and added dropwise over 1 hour to a phenol solution kept at -20 to 15°C.
滴下終了後、室温に加温した後、反応後を水１
中に注入すると黄色油状物が沈澱する。この油
状物をトルエン500ｇに溶解し、水と重炭酸ナト
リウムで洗浄した後、濃縮するとポリチオビスフ
エノールが黄色油状物として得られる。 After the dropwise addition is complete, warm to room temperature, and add 1 liter of water after the reaction.
When injected into the solution, a yellow oil precipitates out. This oil is dissolved in 500 g of toluene, washed with water and sodium bicarbonate, and concentrated to give the polythiobisphenol as a yellow oil.
ポリチオビスフエノールを亜鉛末と塩酸により
定量的に還元し、対応するチオールに変換してガ
スクロマトグラフイにより分析した結果、ポリチ
オビスフエノールの収率は81.2％であり、不純物
としてモノスルフイドが4.9％含まれていた。 Polythiobisphenol was quantitatively reduced with zinc dust and hydrochloric acid, converted to the corresponding thiol, and analyzed by gas chromatography. The yield of polythiobisphenol was 81.2%, with 4.9% monosulfide as an impurity. It was included.
４，4´−ポリチオビスメタンスルホニルオキシ
ベンゼン
ポリチオビスフエノール138.8ｇ（フエノール
１モル分）を酢酸エチル200ｇに溶解し、５℃に
冷却する。メタンスルホニルクロリド114.5ｇ
（１モル）を酢酸エチル100ｇに溶解し、５℃、５
分間でポリチオビスフエノール溶液に滴下する。
さらに、トリエチルアミン101.2ｇ（１モル）を
酢酸エチル100ｇに溶解し、５℃、45分間で反応
液に適下する。滴下終了後室温に加温した後、生
成したトリエチルアミン塩酸塩の沈澱を濾過によ
り除き、酢酸エチルを留去すると４，4′−ポリチ
オビス（メタンスルホニルオキシベンゼン）
221.5ｇが黄色油状物として得られる。この４，
4′−ポリチオビスメタンスルホニルオキシベンゼ
ンを亜鉛末と塩酸により定量的に還元して対応す
るチオールに変換して液体クロマトグラフイによ
り分析した結果、４，4′−ポリチオビス（メタン
スルホニルオキシベンゼン）の収率は80.8％（フ
エノール基準）であり、不純物はモノスルフイド
が7.2％含まれていた。4,4'-Polythiobismethanesulfonyloxybenzene 138.8 g of polythiobisphenol (1 mole of phenol) is dissolved in 200 g of ethyl acetate and cooled to 5°C. Methanesulfonyl chloride 114.5g
(1 mol) was dissolved in 100 g of ethyl acetate, and
Add dropwise to the polythiobisphenol solution for minutes.
Furthermore, 101.2 g (1 mole) of triethylamine was dissolved in 100 g of ethyl acetate, and the solution was added to the reaction solution at 5° C. for 45 minutes. After the completion of the dropwise addition and warming to room temperature, the precipitate of triethylamine hydrochloride formed was removed by filtration, and ethyl acetate was distilled off, yielding 4,4'-polythiobis(methanesulfonyloxybenzene).
221.5 g are obtained as a yellow oil. This 4,
4'-Polythiobismethanesulfonyloxybenzene was quantitatively reduced with zinc dust and hydrochloric acid to convert it to the corresponding thiol and analyzed by liquid chromatography. As a result, it was found that 4,4'-polythiobis(methanesulfonyloxybenzene) The yield was 80.8% (based on phenol), and the impurity contained 7.2% monosulfide.
４−（メタンスルホニルオキシ）チオフエノー
ル
４，4′−ポリチオビスメタンスルホニルオキシ
ベンゼン221.5ｇ（フエノール１モル分）をメタ
ノール500ｇに溶解し、亜鉛末52.3ｇ（0.8モル）
を加えて加熱し還流させる。35％塩酸156.4ｇ
（1.5モル）を１時間で添加し、さらに２時間還流
温度を保つ。反応後、メタノールを濃縮しトルエ
ンで抽出する。トルエン層を10％苛性ソーダ水溶
液500ｇで抽出し、得られた水層に35％塩酸を加
えて酸性化し、トルエンで抽出する。トルエン層
からトルエンを留去すると４−（メタンスルホニ
ルオキシ）チオフエノールの白色結晶148.6ｇが
得られてる。液体クロマトグラフイによる分析か
ら純度97.5収率70.9％（フエノール基準）であ
る。四％塩化炭素から再結晶すると４−（メタン
スルホニルオキシ）チオフエノールの白色結晶
142.6ｇが得られる。液体クロマトグラフイによ
る分析から純度98.4％、収率68.7％（フエノール
基準）である。融点61℃である。 4-(Methanesulfonyloxy)thiophenol Dissolve 221.5 g (1 mole of phenol) of 4,4'-polythiobismethanesulfonyloxybenzene in 500 g of methanol, and dissolve 52.3 g (0.8 mole) of zinc powder.
Add and heat to reflux. 35% hydrochloric acid 156.4g
(1.5 mol) is added in 1 hour and kept at reflux temperature for a further 2 hours. After the reaction, methanol is concentrated and extracted with toluene. The toluene layer is extracted with 500 g of 10% caustic soda aqueous solution, the resulting aqueous layer is acidified by adding 35% hydrochloric acid, and extracted with toluene. When toluene was distilled off from the toluene layer, 148.6 g of white crystals of 4-(methanesulfonyloxy)thiophenol were obtained. Analysis by liquid chromatography shows that the purity is 97.5 and the yield is 70.9% (based on phenol). Recrystallization from 4% carbon chloride gives white crystals of 4-(methanesulfonyloxy)thiophenol.
142.6g is obtained. Analysis by liquid chromatography shows that the purity is 98.4% and the yield is 68.7% (based on phenol). Melting point is 61℃.
［発明の効果］
本発明の製造方法によれば、簡便な操作、少な
い工程数、かつ高収率で工業的に有利に４−（メ
タンスルホニルオキシ）チオフエノールを得るこ
とができる。[Effects of the Invention] According to the production method of the present invention, 4-(methanesulfonyloxy)thiophenol can be obtained industrially advantageously with a simple operation, a small number of steps, and a high yield.
Claims (1)
還元することを特徴とする４−（メタンスルホニ
ルオキシ）チオフエノールの製法。 ２ メシル化反応をトリエチルアミン触媒の存在
下に行なう特許請求の範囲１記載の方法。[Claims] 1. After mesylating polythiobisphenol,
A method for producing 4-(methanesulfonyloxy)thiophenol, which is characterized by reduction. 2. The method according to claim 1, wherein the mesylation reaction is carried out in the presence of a triethylamine catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60049165A JPS61207370A (en) | 1985-03-11 | 1985-03-11 | Production of 4-(methanesulfonyloxy)thiophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60049165A JPS61207370A (en) | 1985-03-11 | 1985-03-11 | Production of 4-(methanesulfonyloxy)thiophenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61207370A JPS61207370A (en) | 1986-09-13 |
| JPH0425946B2 true JPH0425946B2 (en) | 1992-05-06 |
Family
ID=12823467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60049165A Granted JPS61207370A (en) | 1985-03-11 | 1985-03-11 | Production of 4-(methanesulfonyloxy)thiophenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61207370A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4750337B2 (en) * | 2000-06-08 | 2011-08-17 | 株式会社カネカ | Method for producing sulfonate ester |
| EP2399904A1 (en) * | 2010-05-26 | 2011-12-28 | Nabriva Therapeutics AG | Process for the preparation of pleuromutilins |
| CN105980354B (en) * | 2014-02-13 | 2018-04-13 | 组合化学工业株式会社 | The manufacture method and its intermediate of pest control agent |
-
1985
- 1985-03-11 JP JP60049165A patent/JPS61207370A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61207370A (en) | 1986-09-13 |
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