JPS6354355A - Production of aromatic thiol - Google Patents
Production of aromatic thiolInfo
- Publication number
- JPS6354355A JPS6354355A JP62132052A JP13205287A JPS6354355A JP S6354355 A JPS6354355 A JP S6354355A JP 62132052 A JP62132052 A JP 62132052A JP 13205287 A JP13205287 A JP 13205287A JP S6354355 A JPS6354355 A JP S6354355A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- parts
- carbon tetrachloride
- formula
- sulfonic acid
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- -1 aromatic thiol Chemical class 0.000 title abstract description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RLDSFBXSHHFHGA-UHFFFAOYSA-N 1-methoxy-4-[(4-methoxyphenyl)diselanyl]benzene Chemical compound C1=CC(OC)=CC=C1[Se][Se]C1=CC=C(OC)C=C1 RLDSFBXSHHFHGA-UHFFFAOYSA-N 0.000 description 1
- PZQGLCGLPMWYBT-UHFFFAOYSA-N 1-methoxy-4-[(4-methoxyphenyl)disulfanyl]benzene Chemical compound C1=CC(OC)=CC=C1SSC1=CC=C(OC)C=C1 PZQGLCGLPMWYBT-UHFFFAOYSA-N 0.000 description 1
- NIFAOMSJMGEFTQ-UHFFFAOYSA-N 4-methoxybenzenethiol Chemical compound COC1=CC=C(S)C=C1 NIFAOMSJMGEFTQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene 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
- Catalysts (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】
本発明は芳香族チオールの製５永に係わる。詳記すわば
、式 Ａ −Ｓ ０３Ｒ−＋ Ａ −Ｓ Ｉｆ （Ａは
置換基をもった、或はもたない芳香環残基、Ｒは水素、
アルカリ金属、またはアルキル基を表わす。以下間し、
）で示される合成反応を、基質である芳香族スルホン酸
類Ａ−５Ｏ，Ｒに、還元助剤の存在で、トリフェニルホ
スフィンを反応させて達成する、芳香族チオールＡ−５
）ｌの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of aromatic thiols. In detail, the formula A -S 03R-+ A -S If (A is an aromatic ring residue with or without a substituent, R is hydrogen,
Represents an alkali metal or an alkyl group. Between the following,
) is achieved by reacting the aromatic sulfonic acids A-5O,R as a substrate with triphenylphosphine in the presence of a reducing agent.
) l.
芳香族チオールは医薬品その他工業的製品及びそわらの
原料、中間体として有用であるか、その効果的な製法は
乏しく、而も本発明方法の如くワン・ポット反応で簡易
に高純度の製品を、好収率で得る方法はなかった。Aromatic thiols are useful as raw materials and intermediates for pharmaceuticals and other industrial products, as well as soft straw, but there are few effective methods for producing them. There was no way to obtain it with a good yield.
本発明者らは鋭意研究の結果、人手し易い基質であり乍
ら、還元反応に抵抗して原料とし難い芳香族スルホン酸
類から、有用な芳香族チオールを得る新規簡易な製法を
開発、本発明を完成した。As a result of intensive research, the present inventors have developed a new and simple manufacturing method for obtaining useful aromatic thiols from aromatic sulfonic acids, which are easy-to-handle substrates but are difficult to use as raw materials because they resist reduction reactions. completed.
従来芳香族チオールは、製造困難な原料、例えばリチウ
ム化合物、むしろチオールが原料となるような化合物、
例えばチオールエステルなどからの製法が知られていた
り、梢々製造し易いハロゲン化合物とかスルホン酸クロ
リドからの、扱い難く収率低い製法が行われていたに過
ぎない。Conventionally, aromatic thiols are made from raw materials that are difficult to produce, such as lithium compounds, or rather compounds where thiols are the raw material.
For example, production methods using thiol esters have been known, while methods using halogen compounds or sulfonic acid chlorides, which are easy to produce, are difficult to handle and have low yields.
本発明方法は、適当な有機溶剤中、芳香族スルホン酸類
Ａ−５ｏ３Ｒと、トリフェニルホスフィンと、及び、芳
香族ジスルフィド、芳香族ジセレニト、四塩化炭素から
成る群から選ばれた還元助剤とを混じて数時間、室温〜
加熱状態で反応すわばよい。基質として芳香族スルホン
酸のアルカリ金属塩またはアルキルエステルを選んだと
きは、上記反応の後、重量の水を添加して、更に少時加
熱するという付帯処理を施す。収量は定量的である。The method of the present invention comprises combining aromatic sulfonic acids A-5o3R, triphenylphosphine, and a reducing agent selected from the group consisting of aromatic disulfides, aromatic diselenites, and carbon tetrachloride in a suitable organic solvent. Mix at room temperature for several hours
It is sufficient to react under heating. When an alkali metal salt or alkyl ester of an aromatic sulfonic acid is selected as a substrate, after the above reaction, additional treatment is performed by adding a weight of water and further heating for a short time. Yield is quantitative.
使用する４１機溶剤は原料類を溶解し、本発明方法条件
で原料類及び成績体と反応しないなら、通常のものが支
障なく使用できる。経済的見地からベンゼン、トルエン
、キシレン、ヘキサン、ヘプタンなどが好ましい。As long as the solvent to be used dissolves the raw materials and does not react with the raw materials and the resultant under the process conditions of the present invention, ordinary solvents can be used without any problem. From an economic standpoint, benzene, toluene, xylene, hexane, heptane, etc. are preferred.
スルホン酸基１個について示せば、その基質１モルに対
して、トリフェニルホスフィンは当量である３モル−若
干過剰に使用、還元助剤は触媒として作用するから数量
は特に規定されないが、使用量を減らすと、反応時間が
若干延びる結果となる。通常０．１〜１モルを使用する
。芳香族ジスルフィドまたは芳香族ジセレニドを用いる
場合は、その芳香環残基は、基質として採用した芳香族
スルホン酸類の芳香環残基と、同じものを使用するのが
便利である。For one sulfonic acid group, per mole of the substrate, triphenylphosphine is used in an equivalent amount of 3 moles - slightly in excess.As the reduction aid acts as a catalyst, the quantity is not particularly specified, but the amount used is Reducing the results in slightly longer reaction times. Usually 0.1 to 1 mol is used. When aromatic disulfide or aromatic diselenide is used, it is convenient to use the same aromatic ring residue as that of the aromatic sulfonic acid used as the substrate.
反応終了すれば稀ハイドロサルファイド水溶液で洗浄後
、アルカリ水溶液へ成績チオールを移して中和してチオ
ールを単離、有機溶剤で抽出して特製する。一般にチオ
ール類は空気等によって酸化さね易いので、不活性ガス
雰囲気内で処理を終るのが望ましい。アルカリ水溶液不
溶分として回収されるトリフェニルホスフィンオキシト
は、還元してトリフェニルホスフィンに再生される。After the reaction is completed, the thiol is washed with a dilute aqueous hydrosulfide solution, then transferred to an alkaline aqueous solution to neutralize it, and the thiol is isolated and extracted with an organic solvent to produce a special product. Generally, thiols are not easily oxidized by air or the like, so it is desirable to complete the treatment in an inert gas atmosphere. Triphenylphosphine oxyto, which is recovered as an aqueous alkali solution insoluble matter, is reduced and regenerated into triphenylphosphine.
以下に実施例を示す。数量を表わす部は重量部を、％は
重量％を表わす。Examples are shown below. Parts representing numbers represent parts by weight, and % represents weight %.
実施例１゜
ベンゼン６００部に四塩化炭素５．４部とトリフェニル
ホスフィン１０５部を添加、ベンゼンスルホン酸１５．
８部を加えて３時間還流して反応する。冷却後３％ハイ
ドロ亜硫酸ナトリウム水溶液４００部で洗浄（窒素雰囲
気中）、５％水酸化ナトリウム水溶液８００部次いで２
００部で抽出、アルカリ抽出水溶液を酸で中和して、分
層して来る有機化合物を、エーテルで抽出分取する。Example 1 5.4 parts of carbon tetrachloride and 105 parts of triphenylphosphine were added to 600 parts of benzene, and 15.0 parts of benzenesulfonic acid was added.
Add 8 parts and react by refluxing for 3 hours. After cooling, washing with 400 parts of a 3% aqueous sodium hydrosulfite solution (in a nitrogen atmosphere), followed by 800 parts of a 5% aqueous sodium hydroxide solution, followed by 2
The aqueous alkaline extraction solution is neutralized with acid, and the resulting organic compound is extracted and fractionated with ether.
エーテル溶液を乾燥後分溜、沸点７５〜７℃（３０ｍｄ
ｇ）のチオフェノール１０．０部を得る。The ether solution was dried and then fractionated, boiling point 75-7℃ (30md
g) 10.0 parts of thiophenol are obtained.
四塩化炭素の代りにジフェニルジスルフィド７．６部を
使っても同様の結果を得る。但しジフェニルジスルフィ
ドを使う場合、ジフェニルジスルフィドの還元反応も副
生するので、チオフェノールの収得量は上昇する。Similar results are obtained by using 7.6 parts of diphenyl disulfide in place of carbon tetrachloride. However, when diphenyl disulfide is used, the reduction reaction of diphenyl disulfide also produces a by-product, so the yield of thiophenol increases.
実施例２゜
ベンゼン５００部、０−ブロムベンゼンスルホン酸２３
．７部、四塩化炭素４．５部、トリフェニルホスフィン
１１０部を用い、６時間還流反応したあと、実施例１と
同様にして、沸点１１５〜８℃（１８ｍｄｇ）の０−ブ
ロムチオフェノール１６．８部を得る。Example 2 500 parts of benzene, 23 parts of 0-bromobenzenesulfonic acid
．． After refluxing for 6 hours using 7 parts of carbon tetrachloride, 4.5 parts of carbon tetrachloride, and 110 parts of triphenylphosphine, 16.0 parts of 0-bromothiophenol having a boiling point of 115 to 8°C (18 mdg) was added in the same manner as in Example 1. Get 8 copies.
実施例３゜
ベンゼン５００部、ρ−メトキシベンゼンスルホン酸エ
ヂル２１゜６部、四塩化炭素９．１部、トリフェニルホ
スフィン１００部を用い、１０ 分間ａ流反応したあと
、水２部と相溶助剤のジオキサン２０部とを加えて、１
０分間還流する。以下実施例１と同様にして、沸点８６
〜９℃（５＋＋＋＋ｎＨｇ）のｐ−メトキシチオフェノ
ール１２．７部を得る。Example 3 500 parts of benzene, 21.6 parts of ρ-methoxybenzenesulfonate, 9.1 parts of carbon tetrachloride, and 100 parts of triphenylphosphine were subjected to a flow reaction for 10 minutes, and then mixed with 2 parts of water. Adding 20 parts of dioxane as an auxiliary agent, 1
Reflux for 0 minutes. Hereinafter, in the same manner as in Example 1, boiling point 86
12.7 parts of p-methoxythiophenol are obtained at ~9°C (5+++nHg).
四塩化炭素の代りにｐ−メトキシフェニルジスルフィド
１６．４部、またはｐ−メトキシフェニルジセレニド２
１．９部を使っても全く同じ結果を得る。16.4 parts of p-methoxyphenyl disulfide or 2 parts of p-methoxyphenyl diselenide in place of carbon tetrachloride
Exactly the same result is obtained using 1.9 parts.
Claims (1)
た或はもたない芳香環残基、Ｒは水素、アルカリ金属、
アルキル基を示す。）で表わされる反応において、芳香
族スルホン酸類にトリフェニルホスフィンと、芳香族ジ
スルフィド、芳香族ジセレニド、四塩化炭素から成る群
から選ばれた還元助剤とを反応させることを特徴とする
、芳香族チオールの製造法。(1) Formula A・SO_3R→A・SH (A is an aromatic ring residue with or without a substituent, R is hydrogen, an alkali metal,
Indicates an alkyl group. ), the aromatic sulfonic acid is reacted with triphenylphosphine and a reducing agent selected from the group consisting of aromatic disulfide, aromatic diselenide, and carbon tetrachloride. Method for producing thiol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62132052A JPS6354355A (en) | 1987-05-28 | 1987-05-28 | Production of aromatic thiol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62132052A JPS6354355A (en) | 1987-05-28 | 1987-05-28 | Production of aromatic thiol |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55137956A Division JPS5762252A (en) | 1980-10-02 | 1980-10-02 | Preparation of aromatic thiol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6354355A true JPS6354355A (en) | 1988-03-08 |
| JPH029025B2 JPH029025B2 (en) | 1990-02-28 |
Family
ID=15072396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62132052A Granted JPS6354355A (en) | 1987-05-28 | 1987-05-28 | Production of aromatic thiol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6354355A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531978A (en) * | 2011-12-29 | 2012-07-04 | 浙江大学 | Preparation method of thiophenol |
| CN102584651A (en) * | 2011-12-29 | 2012-07-18 | 浙江大学 | Reduction method of sulfoacid |
-
1987
- 1987-05-28 JP JP62132052A patent/JPS6354355A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531978A (en) * | 2011-12-29 | 2012-07-04 | 浙江大学 | Preparation method of thiophenol |
| CN102584651A (en) * | 2011-12-29 | 2012-07-18 | 浙江大学 | Reduction method of sulfoacid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH029025B2 (en) | 1990-02-28 |
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