JPH029026B2 - - Google Patents
Info
- Publication number
- JPH029026B2 JPH029026B2 JP62132053A JP13205387A JPH029026B2 JP H029026 B2 JPH029026 B2 JP H029026B2 JP 62132053 A JP62132053 A JP 62132053A JP 13205387 A JP13205387 A JP 13205387A JP H029026 B2 JPH029026 B2 JP H029026B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- triphenylphosphine
- reaction
- aromatic
- 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.)
- Expired - Lifetime
Links
- -1 aromatic thiol Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims 1
- 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 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- APDUDRFJNCIWAG-UHFFFAOYSA-N 4-propan-2-ylbenzenethiol Chemical compound CC(C)C1=CC=C(S)C=C1 APDUDRFJNCIWAG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- AAPAGLBSROJFGM-UHFFFAOYSA-N naphthalene-1,5-dithiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1S AAPAGLBSROJFGM-UHFFFAOYSA-N 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WDODWFPDZYSKIA-UHFFFAOYSA-N benzeneselenol Chemical compound [SeH]C1=CC=CC=C1 WDODWFPDZYSKIA-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- MMFBQHXDINNBMW-UHFFFAOYSA-N n,n-dipropylaniline Chemical compound CCCN(CCC)C1=CC=CC=C1 MMFBQHXDINNBMW-UHFFFAOYSA-N 0.000 description 2
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QPCOVAAQWGYTBB-UHFFFAOYSA-N cyclohexane-1,1-disulfonic acid Chemical compound OS(=O)(=O)C1(S(O)(=O)=O)CCCCC1 QPCOVAAQWGYTBB-UHFFFAOYSA-N 0.000 description 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004904 shortening Methods 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
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Description
【発明の詳細な説明】
本発明は芳香族チオールの製法に係わる。詳記
すれば、式Ａ・SO3R→Ａ・SH（Ａはアリール基
を示し、Ｒは水素原子、アルカリ金属原子又はア
ルキル基を示す。以下同じ。）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・SO3R
に、還元助剤の存在で、トリフエニルホスフイン
を反応させて達成する、芳香族チオールＡ・SH
の製造法に於て、この反応系に有機塩基を共存さ
せて、反応時間を著しく短縮する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing aromatic thiols. Specifically, the synthesis reaction represented by the formula A・SO 3 R→A・SH (A represents an aryl group, R represents a hydrogen atom, an alkali metal atom, or an alkyl group; the same applies hereinafter) is carried out using a substrate. Certain aromatic sulfonic acids A・SO 3 R
Aromatic thiol A/SH is achieved by reacting triphenylphosphine in the presence of a reducing aid.
The present invention relates to a method for significantly shortening the reaction time by coexisting an organic base in the reaction system.
芳香族チオールは医薬品その他工業的製品及び
それらの原料、中間体として有用であるが、その
効果的な製法は乏しく、而も本発明方法の如くワ
ン・ポツト反応で簡易に高純度の製品を、好収率
で得る方法はなかつた。 Aromatic thiols are useful as pharmaceuticals and other industrial products, as well as their raw materials and intermediates, but there are few effective methods for producing them, and it is difficult to easily produce high-purity products using a one-pot reaction such as the method of the present invention. There was no way to obtain it with good yield.
本発明者らは鋭意研究の結果、入手し易い基質
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 production method for obtaining useful aromatic thiols from aromatic sulfonic acids, which are easily available substrates but are difficult to use as raw materials due to their resistance to 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、稍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。 Traditionally, aromatic thiols have been manufactured using difficult-to-manufacture raw materials such as lithium compounds, or compounds that use thiols as raw materials, such as thiol esters, or from halogen compounds or sulfonic acid chlorides that are somewhat easy to manufacture. However, only a difficult-to-handle and low-yield manufacturing method was used.
本発明方法は、適当な有機溶剤中、芳香族スル
ホン酸類Ａ・SO3Rと、トリフエニルホスフイン
と、及び、ヨウ素、アリールジスルフイド、アル
コキシ置換アリールジスルフイド、アリールジセ
レニド、アルコキシ置換アリールジセレニド、四
塩化炭素から成る群から選ばれた還元助剤とを有
機塩基の存在下、混じて20分間、室温〜加熱状態
で反応すればよい。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、僅量の水を添加して、
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 involves combining aromatic sulfonic acids A.SO 3 R, triphenylphosphine, and iodine, aryl disulfide, alkoxy-substituted aryl disulfide, aryl diselenide, alkoxy A substituted aryl diselenide and a reducing agent selected from the group consisting of carbon tetrachloride may be mixed in the presence of an organic base and reacted for 20 minutes at room temperature to heated conditions. When an alkali metal salt or alkyl ester of aromatic sulfonic acid is selected as a substrate, a small amount of water is added after the above reaction,
Further, an additional treatment of heating for a short time is performed. Yield is quantitative.
使用する有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 organic solvent 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 organic 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、トリフエニルホスフインは当量で
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限定されないが、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
フイ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, its substrate 1
Based on the mole, triphenylphosphine is used in an equivalent amount of 3 moles to a slight excess.Since the reduction aid acts as a catalyst, the amount is not particularly limited, but if the amount used is reduced, the reaction time will be slightly extended. Become. Usually 0.1 to 1 mole is used. When using aromatic disulfide or aromatic diselenide,
It is convenient to use the same aromatic ring residue as that of the aromatic sulfonic acid used as the substrate.
有機塩基はトリアルキルアミン類、Ｎ，Ｎ−ジ
アルキルアニリン類など通常のものを、基質であ
るスルホン酸に対して通常当量を使用する。 As the organic base, common ones such as trialkylamines and N,N-dialkylanilines are used in an equivalent amount to the sulfonic acid substrate.
反応終了すれば稀ハイドロサルフアイト水溶液
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
精製する。一般にチオール類は空気等によつて酸
化され易いので、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
収されるトリフエニルホスフインオキシドは、還
元してトリフエニルホスフインに再生される。 When the reaction is completed, the resulting thiol is washed with a dilute aqueous hydrosulfite solution, then transferred to an alkaline aqueous solution to neutralize it, and the thiol is isolated and purified by extraction with an organic solvent. Since thiols are generally easily oxidized by air, it is desirable to complete the treatment in an inert gas atmosphere. Triphenylphosphine oxide, 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
トルエン500部にヨウ素5.1部、トリフエニルホ
スフイン120部、トリ−ｎ−ブチルアミン18.5部
を添加、ｐ−イソプロピルベンゼンスルホン酸
20.0部を加えて20分間還流、反応させた。冷却後
３％ハイドロ亜硫酸ナトリウム水溶液500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200部で抽出、アルカリ抽出水溶
液を酸で中和して、分離して来る有機化合物を、
エーテルで抽出分取した。エーテル溶液を乾燥後
分溜、沸点102〜４℃（14mmHg）のｐ−イソプロ
ピルチオフエノール13.6部を得た。Example 1 5.1 parts of iodine, 120 parts of triphenylphosphine, and 18.5 parts of tri-n-butylamine were added to 500 parts of toluene, p-isopropylbenzenesulfonic acid
20.0 parts was added and the mixture was refluxed and reacted for 20 minutes. After cooling, wash with 500 parts of a 3% sodium hydrosulfite aqueous solution (in a nitrogen atmosphere), extract with 800 parts of a 5% sodium hydroxide aqueous solution, then 200 parts, neutralize the alkaline extraction aqueous solution with an acid, and separate organic compounds. of,
It was extracted and fractionated with ether. The ether solution was dried and then fractionated to obtain 13.6 parts of p-isopropylthiophenol having a boiling point of 102-4°C (14mmHg).
比較例 １
トルエン500部、ｐ−イソプロピルベンゼンス
ルホン酸20.0部、ヨウ素5.1部及びトリフエニル
ホスフイン120部を用い、５時間還流反応したあ
と、実施例１と同様にして、沸点102〜４℃（14
mmHg）のｐ−イソプロピルチオフエノール13.6
部を得た。Comparative Example 1 After 5 hours of reflux reaction using 500 parts of toluene, 20.0 parts of p-isopropylbenzenesulfonic acid, 5.1 parts of iodine and 120 parts of triphenylphosphine, the boiling point was 102 to 4°C ( 14
mmHg) p-isopropylthiophenol 13.6
I got the department.
実施例 ２
トルエン500部にｐ−イソプロピルベンゼンス
ルホン酸20.0部、ジ−ｐ−クミルジスルフイド
6.1部、トリフエニルホスフイン120部及びトリ−
ｎ−ブチルアミン18.5部を加え、20分間還流反応
させた。反応後、実施例１と同様に処理して、沸
点101〜３℃（14mmHg）のｐ−イソプロピルチオ
フエノール14.0部を得た。Example 2 20.0 parts of p-isopropylbenzenesulfonic acid and di-p-cumyl disulfide in 500 parts of toluene
6.1 parts, 120 parts of triphenylphosphine and tri-
18.5 parts of n-butylamine was added, and the mixture was refluxed for 20 minutes. After the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 14.0 parts of p-isopropylthiophenol having a boiling point of 101 to 3°C (14 mmHg).
比較例 ２
トルエン500部、ｐ−イソプロピルベンゼンス
ルホン酸20.0部、ジ−ｐ−クミルジスルフイド
6.1部及びトリフエニルホスフイン120部を用い、
５時間還流反応したあと、実施例２と同様にし
て、沸点101〜３℃（14mmHg）のｐ−イソプロピ
ルチオフエール13.9部を得た。Comparative Example 2 500 parts of toluene, 20.0 parts of p-isopropylbenzenesulfonic acid, di-p-cumyl disulfide
using 6.1 parts and 120 parts of triphenylphosphine,
After refluxing for 5 hours, 13.9 parts of p-isopropylthiophyl having a boiling point of 101 to 3°C (14 mmHg) was obtained in the same manner as in Example 2.
実施例 ３
トルエン500部にｐ−イソプロピルベンゼンス
ルホン酸20.0部、四塩化炭素3.1部、トリフエニ
ルホスフイン120部及びトリ−ｎ−ブチルアミン
18.5部を加え、20分間還流反応させた。反応後、
実施例１と同様に処理して、沸点102〜４℃（14
mmHg）のｐ−イソプロピルチオフエノール13.5
部を得た。Example 3 20.0 parts of p-isopropylbenzenesulfonic acid, 3.1 parts of carbon tetrachloride, 120 parts of triphenylphosphine, and tri-n-butylamine in 500 parts of toluene.
18.5 parts were added and the mixture was refluxed for 20 minutes. After the reaction,
It was treated in the same manner as in Example 1, and the boiling point was 102-4℃ (14℃).
mmHg) p-isopropylthiophenol 13.5
I got the department.
比較例 ３
トルエン500部、ｐ−イソプロピルベンゼンス
ルホン酸20.0部、四塩化炭素3.1部及びトリフエ
ニルホスフイン120部を用い、５時間還流反応し
たあと、実施例３と同様にして、沸点102〜４℃
（14mmHg）のｐ−イソプロピルチオフエノール
13.6部を得た。Comparative Example 3 After 5 hours of reflux reaction using 500 parts of toluene, 20.0 parts of p-isopropylbenzenesulfonic acid, 3.1 parts of carbon tetrachloride and 120 parts of triphenylphosphine, the boiling point was 102 to 4 in the same manner as in Example 3. ℃
(14mmHg) of p-isopropylthiophenol
Got 13.6 copies.
実施例 ４
シクロヘキサン800部にナフタレン−１，５−
ジスルホン酸28.8部、ヨウ素20部、トリフエニル
ホスフイン200部及びＮ，Ｎ−ジ−ｎ−プロピル
アニリン35.4部を加え、15分間還流反応させた。
反応後、実施例１と同様に処理してエーテル溜去
残をとり、ベンゼンから再結晶して、融点118〜
９℃のナフタレン−１，５−ジチオール17.1部を
得た。Example 4 Naphthalene-1,5- to 800 parts of cyclohexane
28.8 parts of disulfonic acid, 20 parts of iodine, 200 parts of triphenylphosphine, and 35.4 parts of N,N-di-n-propylaniline were added, followed by a reflux reaction for 15 minutes.
After the reaction, the same procedure as in Example 1 was carried out to remove the ether distillation residue, which was recrystallized from benzene to give a melting point of 118~
17.1 parts of naphthalene-1,5-dithiol at 9°C was obtained.
比較例 ４
シクロヘキサン800部、ナフタレン−１，５−
ジスルホン酸28.8部、ヨウ素20部及びトリフエニ
ルホスフイン200部を用い、４時間還流反応した
あと、実施例４と同様にしてエーテル溜去残をと
り、ベンゼンから再結晶して、融点118〜９℃の
ナフタレン−１，５−ジチオール16.9部を得た。Comparative Example 4 800 parts of cyclohexane, naphthalene-1,5-
After refluxing for 4 hours using 28.8 parts of disulfonic acid, 20 parts of iodine, and 200 parts of triphenylphosphine, the ether distillation residue was collected in the same manner as in Example 4, and recrystallized from benzene to give a product with a melting point of 118-9. 16.9 parts of naphthalene-1,5-dithiol were obtained.
実施例 ５
シクロヘキサン800部にナフタレン−１，５−
ジスルホン酸28.8部、ジフエニルジセレニド21.8
部、トリフエニルホスフイン200部及びＮ，Ｎ−
ジ−ｎ−プロピルアニリン35.4部を加え、15分間
還流反応させた。反応後、実施例１と同様に処理
してエーテル溜去後、更にジフエニルジセレニド
が還元して副生するセレノフエノール（沸点183
℃）を溜去してその残渣をとり、ベンゼンから再
結晶して、融点117〜９℃のナフタレン−１，５
−ジチオール16.6部を得た。Example 5 Naphthalene-1,5- to 800 parts of cyclohexane
Disulfonic acid 28.8 parts, diphenyl diselenide 21.8 parts
parts, 200 parts of triphenylphosphine and N,N-
35.4 parts of di-n-propylaniline was added, and the mixture was refluxed for 15 minutes. After the reaction, the same procedure as in Example 1 was carried out to remove the ether, and diphenyl diselenide was further reduced to produce selenophenol (boiling point 183
) was distilled off, the residue was recrystallized from benzene, and naphthalene-1,5 having a melting point of 117-9°C was obtained.
-16.6 parts of dithiol were obtained.
比較例 ５
シクロヘキサン800部、ナフタレン−１，５−
ジスルホン酸28.8部、ジフエニルジセレニド21.8
部及びトリフエニルホスフイン200部を用い、４
時間還流反応したあと、実施例５と同様にしてエ
ーテル溜去後、さらにジフエニルジセレニドが還
元して副生するセレノフエノール（沸点183℃）
を溜去してその残渣をとり、ベンゼンから再結晶
して、融点117〜９℃のナフタレン−１，５−ジ
チオール16.5部を得た。Comparative Example 5 800 parts of cyclohexane, naphthalene-1,5-
Disulfonic acid 28.8 parts, diphenyl diselenide 21.8 parts
4 parts and 200 parts of triphenylphosphine.
After refluxing for a period of time, ether is distilled off in the same manner as in Example 5, and diphenyl diselenide is further reduced to produce selenophenol (boiling point 183°C).
was distilled off, the residue was taken and recrystallized from benzene to obtain 16.5 parts of naphthalene-1,5-dithiol having a melting point of 117-9°C.
Claims (1)
し、Ｒは水素原子、アルカリ金属原子又はアルキ
ル基を示す。］で表わされる反応に於いて、有機
塩基の存在下、芳香族スルホン酸類にトリフエニ
ルホスフインと、ヨウ素、アリールジスルフイ
ド、アルコキシ置換アリールジスルフイド、アリ
ールジセレニド、アルコキシ置換アリールジセレ
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 3 R→A.SH [A represents an aryl group, R represents a hydrogen atom, an alkali metal atom, or an alkyl group. In the reaction represented by 1. A method for producing an aromatic thiol, which comprises reacting it with a reducing aid selected from the group consisting of nitride, carbon tetrachloride, and carbon tetrachloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62132053A JPS6354356A (en) | 1987-05-28 | 1987-05-28 | Production of aromatic thiol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62132053A JPS6354356A (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 |
|---|---|
| JPS6354356A JPS6354356A (en) | 1988-03-08 |
| JPH029026B2 true JPH029026B2 (en) | 1990-02-28 |
Family
ID=15072419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62132053A Granted JPS6354356A (en) | 1987-05-28 | 1987-05-28 | Production of aromatic thiol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6354356A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584651B (en) * | 2011-12-29 | 2013-12-18 | 浙江大学 | Reduction method of sulfoacid |
| WO2023176299A1 (en) * | 2022-03-14 | 2023-09-21 | スガイ化学工業株式会社 | 1,6-naphthalenedithiol and method for producing same |
-
1987
- 1987-05-28 JP JP62132053A patent/JPS6354356A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6354356A (en) | 1988-03-08 |
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