JPH01149762A - Production of 4-(alkylsulfonyl)-2-aminophenol - Google Patents
Production of 4-(alkylsulfonyl)-2-aminophenolInfo
- Publication number
- JPH01149762A JPH01149762A JP62307812A JP30781287A JPH01149762A JP H01149762 A JPH01149762 A JP H01149762A JP 62307812 A JP62307812 A JP 62307812A JP 30781287 A JP30781287 A JP 30781287A JP H01149762 A JPH01149762 A JP H01149762A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- alkylsulfonyl
- formula
- alkylthio
- reaction
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- 238000006396 nitration reaction Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims 3
- 230000002140 halogenating effect Effects 0.000 claims 1
- 229960004592 isopropanol Drugs 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000001546 nitrifying effect Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 5
- SFLMBHYNCSYPOO-UHFFFAOYSA-N 2-amino-4-methylsulfonylphenol Chemical compound CS(=O)(=O)C1=CC=C(O)C(N)=C1 SFLMBHYNCSYPOO-UHFFFAOYSA-N 0.000 description 4
- WPYHDEFQVGUCQZ-UHFFFAOYSA-N 4-(methylsulfonyl)-2-nitrophenol Chemical compound CS(=O)(=O)C1=CC=C(O)C([N+]([O-])=O)=C1 WPYHDEFQVGUCQZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 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
- 239000007858 starting material Substances 0.000 description 4
- QASBCTGZKABPKX-UHFFFAOYSA-N 4-(methylsulfanyl)phenol Chemical compound CSC1=CC=C(O)C=C1 QASBCTGZKABPKX-UHFFFAOYSA-N 0.000 description 3
- KECCFSZFXLAGJS-UHFFFAOYSA-N 4-methylsulfonylphenol Chemical compound CS(=O)(=O)C1=CC=C(O)C=C1 KECCFSZFXLAGJS-UHFFFAOYSA-N 0.000 description 3
- SPWHEQZSUUTOHK-UHFFFAOYSA-N 4-propylsulfanylphenol Chemical compound CCCSC1=CC=C(O)C=C1 SPWHEQZSUUTOHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- UPJVUFCLBYQKFH-UHFFFAOYSA-N 2-amino-4-ethylsulfonylphenol Chemical compound CCS(=O)(=O)C1=CC=C(O)C(N)=C1 UPJVUFCLBYQKFH-UHFFFAOYSA-N 0.000 description 2
- QQDSMYDELYLLGN-UHFFFAOYSA-N 2-amino-4-propan-2-ylsulfonylphenol Chemical compound CC(C)S(=O)(=O)C1=CC=C(O)C(N)=C1 QQDSMYDELYLLGN-UHFFFAOYSA-N 0.000 description 2
- SPSBHCQVKNWJGB-UHFFFAOYSA-N 2-amino-4-propylsulfonylphenol Chemical compound CCCS(=O)(=O)C1=CC=C(O)C(N)=C1 SPSBHCQVKNWJGB-UHFFFAOYSA-N 0.000 description 2
- FMIHFTDZEIOVQX-UHFFFAOYSA-N 4-ethylsulfanylphenol Chemical compound CCSC1=CC=C(O)C=C1 FMIHFTDZEIOVQX-UHFFFAOYSA-N 0.000 description 2
- DVDGHEZGPNPQAV-UHFFFAOYSA-N 4-propan-2-ylsulfanylphenol Chemical compound CC(C)SC1=CC=C(O)C=C1 DVDGHEZGPNPQAV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SOOARYARZPXNAL-UHFFFAOYSA-N 2-(Methylthio)phenol Chemical compound CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 241000277269 Oncorhynchus masou Species 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- -1 ethylene dichloride Chemical compound 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、４−（アルキルスルホニル）−２−アミノフ
ェノールの新規な製造方法に関する。４−（アルキルス
ルホニル）−２−アミノフェノールは、染料の中間体と
して有用な化合物である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel method for producing 4-(alkylsulfonyl)-2-aminophenol. 4-(Alkylsulfonyl)-2-aminophenol is a compound useful as a dye intermediate.
（従来の技術）
従来、４−（アルキルスルホニル）−２−７ミノフエノ
ールを製造する方法はいくつか知られている。例えば、
英国特許第１１２８２１７号には、２−アミノ−４−（
メチルスルホニル）フェノールを三臭化ボロンにより還
元し、２−アミノ−４−（メチルスルホニル）フェノー
ルを得る方法が記載されているが、原料の入手が困難な
うえ、危険性のある三臭化ポロンを使用すること、また
我々の追試試験の結果では、収率が約６５％程度である
こと等から、工業的に有用な方法とはいえない。(Prior Art) Several methods for producing 4-(alkylsulfonyl)-2-7 minophenol have been known. for example,
British Patent No. 1128217 describes 2-amino-4-(
A method to obtain 2-amino-4-(methylsulfonyl)phenol by reducing methylsulfonyl)phenol with boron tribromide is described, but the raw material is difficult to obtain and is dangerous due to the use of boron tribromide. It cannot be said that this is an industrially useful method because of the fact that the method uses
また、Ｃｏｍｐｔｅｓ Ｒａｎｄｕｓ ｄｅ ｌ’Ａｃ
ａｄｅｍｉｅ Ｂｕｌｇａｒｅ ｄｅｓ ５ｃｉｅ
ｎｄｓ １９ （１２） １１５５−８ （１９６
Ｂ）には、ベンゾオキサシロン−５−スルホニルクロラ
イドを還元してベンゾオキサシロン−５−スルフィン酸
とし、ざらにメチル化してベンゾオキサシロン−５−メ
チルスルホンとなし、これを加水分解することにより、
２−アミノ−４−（メチルスルホニル）−フェノールを
１ｑる方法が記載されているが、この方法もまた、原料
が高価なうえ、全体の工程が長いため、工業的に右利な
方法とはいえない。Also, Comptes Randus de l'Ac
ademie bulgare des 5cie
nds 19 (12) 1155-8 (196
B), by reducing benzoxacilone-5-sulfonyl chloride to benzoxacilone-5-sulfinic acid, roughly methylating it to benzoxacilone-5-methylsulfone, and hydrolyzing this. ,
A method for preparing 1 q of 2-amino-4-(methylsulfonyl)-phenol is described, but this method is also not industrially advantageous because the raw materials are expensive and the overall process is long. I can't say that.
（発明が解決しようとする問題点〉
本発明者らは、前記した４−（アルキルスルホニル）−
２−アミノフェノールの工業的に有利な製造方法を見い
出すべく鋭意研究し、工業原料として容易に入手し得る
４−（アルキルチオ）フェノールを用いることに着目し
た。(Problems to be Solved by the Invention) The present inventors have solved the above-mentioned 4-(alkylsulfonyl)-
We conducted extensive research to find an industrially advantageous method for producing 2-aminophenol, and focused on using 4-(alkylthio)phenol, which is easily available as an industrial raw material.
水原料を用いれば、酸化工程、ニトロ化工程。If water raw material is used, oxidation process and nitration process.
還元工程の３工程により、高収率かつ高品質の４−（ア
ルキルスルホニル〉−２−アミノフェノールを′ｔＡ造
することができる。Through the three reduction steps, high yield and high quality 4-(alkylsulfonyl)-2-aminophenol can be produced.
（問題点を解決するための手段）
本発明は、４−（アルキルスルホニル）−２−アミノフ
ェノールの新規な製造方法を提供するものである。(Means for Solving the Problems) The present invention provides a novel method for producing 4-(alkylsulfonyl)-2-aminophenol.
その要旨は、４−（アルキルチオ）フェノールを原料と
し、４−（アルキルスルホニル）−２−アミノフェノー
ルを製造するにあたり、一般式（１）
（式中Ｒは、炭素数１〜３のアルキル基を示す。）で表
わされる４−（アルキルチオ）フェノールを酸化して、
一般式（ＩＩ）
（式中Ｒは、前記と同じである。）
で表わされる４−（アルキルスルホニル）フェノールと
なしこれをニトロ化することにより、一般式（１）
（式中Ｒは、前記と同じである。）
で表わされる４−（アルキルスルホニル）−２−ニトロ
フェノールとし、ざらに還元することを特徴とする
一般式（ＩＶ）
Ｈ
（式中Ｒは、前記と同じである。）
で表わされる４−（アルキルスルホニル）−２−アミノ
フェノールの製造法である。The gist is that when producing 4-(alkylsulfonyl)-2-aminophenol using 4-(alkylthio)phenol as a raw material, the general formula (1) (wherein R represents an alkyl group having 1 to 3 carbon atoms) is used. ) is oxidized to give 4-(alkylsulfonyl)phenol represented by the general formula (II) (wherein R is the same as above), and this is converted into 4-(alkylsulfonyl)phenol represented by the general formula (II) (wherein R is the same as above). 4-(alkylsulfonyl)-2-nitrophenol represented by the general formula (1) (wherein R is the same as above) by reducing the general formula to roughly reduce it. (IV) A method for producing 4-(alkylsulfonyl)-2-aminophenol represented by H (wherein R is the same as above).
４−（アルキルチオ）フェノールは、フェノールのジア
ルキルジスルフィド等によるＳ−アルキル化あるいは、
Ｓ−アルキルチオフェノールをハロゲン化した４−ハロ
チオアニソールの加水分解等により容易に得ることがで
きる。かかる４−（アルキルチオ）フェノールの具体例
としては、４−（メチルチオ）フェノール、４−（エチ
ルチオ）フェノール、４−（ｎ−プロピルチオ）フェノ
ール、４−（ｉｓｏ−プロピルチオ）フェノール等を挙
げることができる。4-(Alkylthio)phenol is produced by S-alkylation of phenol with dialkyl disulfide or the like, or
It can be easily obtained by hydrolysis of 4-halothioanisole, which is a halogenated S-alkylthiophenol. Specific examples of such 4-(alkylthio)phenols include 4-(methylthio)phenol, 4-(ethylthio)phenol, 4-(n-propylthio)phenol, and 4-(iso-propylthio)phenol. .
４−（アルキルスルホニル）フェノールは、４−（アル
キルチオ）フェノールの酸化により容易にしかも高収率
で得ることかできる。4-(Alkylsulfonyl)phenol can be easily obtained in high yield by oxidation of 4-(alkylthio)phenol.
開化剤としては、過酸化水素水１次亜塩素酸ナトリウム
、次亜臭素酸ナトリウム等の次亜ハロゲン酸アルカリ金
属塩等を用いることができるが、通常、工業用として、
市販されている２５〜４０％濃度の過酸化水素水が好適
であり、４−（アルキルチオ）フェノールに対し、２．
０〜２．４倍モルの範囲で使用すると好結果が得られる
。２．０倍モル未満では収率が低下し、２．４倍モルを
超えてもさしたる効果がなく不経済である。As the opening agent, an alkali metal hypohalite salt such as hydrogen peroxide solution, sodium hypochlorite, or sodium hypobromite can be used, but usually for industrial use,
A commercially available hydrogen peroxide solution with a concentration of 25 to 40% is suitable, and has a concentration of 2.5% to 4-(alkylthio)phenol.
Good results are obtained when used in a range of 0 to 2.4 times the mole. If it is less than 2.0 times the mole, the yield will decrease, and if it exceeds 2.4 times the mole, there will be no significant effect and it will be uneconomical.
反応溶媒としては、水、メタノール、エタノール等の低
級アルコール、テトラヒドロフラン、ジオキサン等のエ
ーテル類、酢酸、プロピオン酸等の有機酸およびこれら
の混合物等を用いることができる。As the reaction solvent, water, lower alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, organic acids such as acetic acid and propionic acid, and mixtures thereof can be used.
反応温度は、Ｏ°Ｃ〜７０’Ｃ，好ましくは、２０”０
〜６０℃の範囲に保つ。温度が低すぎると反応速度が遅
く、高すぎると副反応が起こり、収率低下の原因となる
。また反応の際、触媒としてタングステン酸を添加すれ
ば円滑に反応を行なうことができる。タングステン酸塩
としては、タングステン酸ナトリウム、タングステン酸
カリウム等を挙げることができる。タングステン酸塩の
添加量は特に限定されるものではないが、０．０１〜０
．２０モル％の範囲が好適である。添加量が少なすぎる
と効果が表われず、多すぎてもそれに見合う効果は得ら
れない。The reaction temperature is 0°C to 70'C, preferably 20'0
Keep in the range of ~60°C. If the temperature is too low, the reaction rate will be slow; if the temperature is too high, side reactions will occur, causing a decrease in yield. Further, during the reaction, if tungstic acid is added as a catalyst, the reaction can be carried out smoothly. Examples of the tungstate salt include sodium tungstate and potassium tungstate. The amount of tungstate added is not particularly limited, but is 0.01 to 0.
．． A range of 20 mol% is preferred. If the amount added is too small, no effect will be obtained, and if the amount added is too large, no commensurate effect will be obtained.
４−（アルキルスルホニル）−２−二トロフエノールは
、以上の反応により得られた４−（アルキルスルホニル
）フェノールのニトロ化反応により、高収率で得ること
ができる。4-(Alkylsulfonyl)-2-nitrophenol can be obtained in high yield by nitration reaction of 4-(alkylsulfonyl)phenol obtained by the above reaction.
ニトロ化剤としては、通常、硝酸が好適であり、４−（
アルキルスルホニル）フェノールに対し、１．０〜１．
１倍モルの範囲で使用すると好結果が得られる。１．０
倍モル以下では収率が低下し、１．１倍モルを超えると
副生物が生成し、これもまた収率低下の原因となる。As the nitrating agent, nitric acid is usually suitable, and 4-(
alkylsulfonyl)phenol, 1.0 to 1.
Good results can be obtained when used in a 1-fold molar range. 1.0
If it is less than 1.1 times the mole, the yield will decrease, and if it exceeds 1.1 times the mole, by-products will be produced, which also causes a decrease in the yield.
反応溶媒としては、７０〜１００％硫酸、塩化メチレン
、クロロホルム、二塩化エチレン等のハロゲン化炭化水
素等を用いることができる。反応温度はＯ〜３０’Ｃ１
好ましくは、Ｏ′Ｃ〜１０’Ｃの範囲である。温度が低
すぎると反応速度が遅く、高すぎると副反応が起こり収
率が低下する。As the reaction solvent, 70 to 100% sulfuric acid, methylene chloride, chloroform, halogenated hydrocarbons such as ethylene dichloride, etc. can be used. Reaction temperature is O~30'C1
Preferably, it is in the range of O'C to 10'C. If the temperature is too low, the reaction rate will be slow; if the temperature is too high, side reactions will occur and the yield will decrease.
目的とする４−（アルキルスルホニル）−２−アミノフ
ェノールは、以上の反応により得られた４−（アルキル
スルホニル）−２−ニトロフェノールを還元することに
より得ることができる。The target 4-(alkylsulfonyl)-2-aminophenol can be obtained by reducing the 4-(alkylsulfonyl)-2-nitrophenol obtained by the above reaction.
還元方法としては、鉄あるいは亜鉛と共に塩酸あるいは
酢酸等の酸を用いる方法、水硫化ナトリウム、水硫化カ
リウム、硫化ナトリウム、￥ｉＡ化カリウム等を用いる
方法、パラジウム触媒あるいはニッケル触媒等を用いた
水添による方法等、いずれの方法も可能である。Reduction methods include a method using an acid such as hydrochloric acid or acetic acid together with iron or zinc, a method using sodium bisulfide, potassium bisulfide, sodium sulfide, potassium chloride, etc., and hydrogenation using a palladium catalyst or a nickel catalyst. Any method is possible, such as the method by.
特にパラジウム炭素等のパラジウム触媒を用いた水添に
よる方法は常圧で反応でき、しかも好収率で高品質の目
的物を得ることができる。反応溶媒としては、特に限定
されるものではないが、メタノール、エタノール、１ｓ
ｏ−プロパツール等の低級アルコールを用いることがで
きるが、就中１ｓｏ−プロパツールを用いると好結果が
１ｑられる。反応温度は２０’Ｃ〜８０°Ｃ１好ましく
は３０°Ｃ〜７０℃の範囲に保つ。温度が低すぎると反
応速度が遅く、高すぎると副反応が起こり収率が低下す
る。In particular, a hydrogenation method using a palladium catalyst such as palladium on carbon allows the reaction to occur at normal pressure and can provide a high-quality target product in good yield. The reaction solvent is not particularly limited, but includes methanol, ethanol, 1s
Lower alcohols such as o-propertool can be used, but particularly good results are obtained when using 1so-propertool. The reaction temperature is maintained in the range of 20'C to 80C, preferably 30C to 70C. If the temperature is too low, the reaction rate will be slow; if the temperature is too high, side reactions will occur and the yield will decrease.
このようにして得られた４−（アルキルスルホニル）−
２−アミノフェノールとしては、２−アミノ−４−（メ
チルスルホニル）−フェノール。4-(alkylsulfonyl)- thus obtained
As 2-aminophenol, 2-amino-4-(methylsulfonyl)-phenol.
２−アミノ−４−（エチルスルホニル）−フェノール、
２−アミノ−４−（ｎ−プロピルスルホニル）−フェノ
ール、２−アミノ−４−（ｉＳＯ−プロピルスルホニル
）−フェノール等を挙げることができる。2-amino-4-(ethylsulfonyl)-phenol,
Examples include 2-amino-4-(n-propylsulfonyl)-phenol and 2-amino-4-(iSO-propylsulfonyl)-phenol.
（発明の効果）
本発明によれば、工業原料として安価にかつ容易に入手
し得る４−（アルキルチオ）フェノールから酸化、ニト
ロ化および還元の工程を経て容易に目的の４−（アルキ
ルスルホニル）−２−アミノフェノールを製造すること
ができる。(Effects of the Invention) According to the present invention, the desired 4-(alkylsulfonyl)- 2-Aminophenol can be produced.
本発明の方法は、従来の方法に比べて収率が高く、工程
も短いため、工業的に非常にすぐれている。The method of the present invention has a higher yield and shorter steps than conventional methods, so it is industrially superior.
（実施例） 以下、実施例により本発明をより具体的に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例−１
攪拌機２滴下ロート、温度計および冷却器を備えた１９
４つロフラスコに、４−（メチルチオ）フェノール１４
０ｇ（１，０モル）、水２６７！？。Example-1 19 equipped with a stirrer, 2 dropping funnels, a thermometer and a cooler
4-(Methylthio)phenol 14 in 4 flasks
0g (1,0 mol), water 267! ? .
タングステン酸ナトリウム０．３ｇを仕込み、２０℃〜
４０’Ｃの範囲で３１％過鼠化水素水２４１．３ｇ（２
，２モル）を徐々に滴下し、さらに５０’Ｃにて１時間
段拌した。その後、室温まで冷却し、過剰の過酸化水素
を亜＠酸ナトリウムで還元したのち、濃塩酸４ｇを加え
反応液のｐＨを１とし、さらに同温度で１時間攪拌した
。その後、濾過、水洗、乾燥し、白色結晶の４−（メチ
ルスルホニル）フェノール１６５．３９を）ｑた。４−
（メチルチオ）フェノールに対する収率は、９６．１％
であった。Prepare 0.3g of sodium tungstate, 20℃～
241.3 g (2
, 2 mol) was gradually added dropwise, and the mixture was further stirred at 50'C for 1 hour. Thereafter, the mixture was cooled to room temperature, excess hydrogen peroxide was reduced with sodium nitrite, and 4 g of concentrated hydrochloric acid was added to adjust the pH of the reaction mixture to 1, followed by further stirring at the same temperature for 1 hour. Thereafter, it was filtered, washed with water, and dried to yield 165.39 q of white crystals of 4-(methylsulfonyl)phenol. 4-
The yield based on (methylthio)phenol was 96.1%.
Met.
次に、攪拌機１滴下ロート、温度計および冷却器を備え
た１、１！４つロフラスコに、９０％硫酸６２８ｇを仕
込み、これに上記にて得られた４−（メチルスルホニル
）フェノールを添加し、引きつづき９４％硝酸６７．６
ｇ（１，０モル）を５〜１０’Ｃの温度で滴下し、さ
らに同温度で１時間攪拌した。その後、反応液を氷水１
．２ｇ中に注ぎ、析出した結晶を濾過、水洗、乾燥し、
黄色結晶の４−（メチルスルホニル）−２−ニトロフェ
ノール２０７．２！？を得た。４−（メチルスルホニル
）フェノールに対する収率は、９９．３％でおった。Next, 628 g of 90% sulfuric acid was charged into a 1, 1! 4-bottle flask equipped with a stirrer, 1 dropping funnel, a thermometer, and a condenser, and the 4-(methylsulfonyl)phenol obtained above was added to this. , followed by 94% nitric acid 67.6
g (1.0 mol) was added dropwise at a temperature of 5 to 10'C, and the mixture was further stirred at the same temperature for 1 hour. After that, dilute the reaction solution with ice water
．． 2 g, and the precipitated crystals were filtered, washed with water, and dried.
Yellow crystalline 4-(methylsulfonyl)-2-nitrophenol 207.2! ? I got it. The yield based on 4-(methylsulfonyl)phenol was 99.3%.
次に攪拌機、水素ガス導入管、温度計および冷却器を協
えた２ｆ１４つロフラスコに上記にて得られた４−（メ
チルスルホニル）−２−ニトロフェノール、１ｓｏ−プ
ロパツール１．＋１、および５％パラジウム炭素１２３
を仕込み、６０〜７０’Ｃの範囲で水素ガスを所定量導
入した。Next, 4-(methylsulfonyl)-2-nitrophenol obtained above, 1so-propanol 1. +1, and 5% palladium carbon 123
was charged, and a predetermined amount of hydrogen gas was introduced at a temperature in the range of 60 to 70'C.
反応後、５？６パラジウム炭素を回収し、ざらに−部１
ＳＯ−プロパツールを召人した。その後、５°Ｃまで冷
却し析出した精品を）濾過、洗浄、屹燥し、微褐色の２
−アミノ−４−（メチルスルホニル）フェノール１５９
．５ｇを得た。（融点１５９°Ｃ〜１６０’Ｃ）４−（
メチルスルホニル）−２−ニトロフェノールに対する収
率は８９．３％であった。After the reaction, 5-6 palladium on carbon was recovered and
I summoned SO-Proper Tools. After that, the precipitated refined product was cooled to 5°C and filtered, washed, and dried.
-amino-4-(methylsulfonyl)phenol 159
．． 5g was obtained. (melting point 159°C to 160'C) 4-(
The yield based on methylsulfonyl)-2-nitrophenol was 89.3%.
出発原料でめる４−（メチルチオ）フェノールに対する
収率は８５．２％であった。The yield based on the starting material 4-(methylthio)phenol was 85.2%.
実施例−２
出発原料を４−（エチルチオ〉フェノールに変えた以外
は実施例−１と同様の操作を行ない、２−アミノ−４−
（エチルスルホニル）フェノールを得た。４−（エチル
チオ）フェノール、に対する収率は８２．８％であった
。Example-2 The same operation as Example-1 was carried out except that the starting material was changed to 4-(ethylthio>phenol), and 2-amino-4-
(ethylsulfonyl)phenol was obtained. The yield based on 4-(ethylthio)phenol was 82.8%.
実施例−３
出発原お１を４−（ｎ−プロピルチオ）フェノールに変
えた以外は実施例−１と同様の操作を行ない、２−アミ
ノ−４−（ｎ−プロピルスルホニル）フェノールを得た
。（融点１＝１０℃〜１４１°Ｃ）４−（ｎ−プロピル
チオ）−フェノールに対する収率は８５．０％であった
。Example 3 2-amino-4-(n-propylsulfonyl)phenol was obtained by carrying out the same operation as in Example 1 except that starting material 1 was changed to 4-(n-propylthio)phenol. (Melting point 1 = 10°C to 141°C) The yield based on 4-(n-propylthio)-phenol was 85.0%.
実施例−４
出発原お１を４−（ｉｓｏ−プロピルチオ）フェノール
に変えた以外は、実施例−１と同様の操作を行ない、２
−アミノ−４−（ｉｓｏ−プロピルスルホニル）フェノ
ールを得た。（融点１２７°Ｃ〜１２８℃）４−（ｉｓ
ｏ−プロピルチオ）フェノールに対する収率は８２．１
％であった。Example-4 The same operation as Example-1 was carried out except that starting material 1 was changed to 4-(iso-propylthio)phenol, and 2
-Amino-4-(iso-propylsulfonyl)phenol was obtained. (melting point 127°C to 128°C) 4-(is
Yield based on o-propylthio)phenol is 82.1
%Met.
実施例−５
攪拌機、温度計、および冷却器を備えた２、１！４つロ
フラスコに実施例−１の方法により合成した４−（メチ
ルスルホニル）−２−二トロフェノ−ル２５．０ｇ（０
，１１５モル〉と１０％水酸化ナトリウム水溶液９００
ｆｆおよび７０％水硫化ナトリウム６０ｓを仕込み、８
５〜９０’Ｃにて３時間攪拌した。Example-5 25.0 g (0.0 g) of 4-(methylsulfonyl)-2-nitrophenol synthesized by the method of Example-1 was placed in a 2, 1, or 4 flask equipped with a stirrer, a thermometer, and a condenser.
, 115 mol> and 10% aqueous sodium hydroxide solution 900 mol
ff and 70% sodium hydrosulfide 60s, 8
Stirred at 5-90'C for 3 hours.
反応終了後、酢酸で反応液を中和したのち、生成物を酢
酸エチルにより抽出し、ざらに水洗した。After the reaction was completed, the reaction solution was neutralized with acetic acid, and the product was extracted with ethyl acetate and washed roughly with water.
その後、酢酸エチルを濃縮し、残渣を１ｓｏ−プロパツ
ールより再精品することにより、２−アミノ−４−（メ
チルスルホニル）フェノール１６．２９（融点１５９°
Ｃ〜１６０’Ｃ）を得た。Thereafter, the ethyl acetate was concentrated and the residue was purified again using 1so-propanol to obtain 2-amino-4-(methylsulfonyl)phenol 16.29 (melting point 159°).
C-160'C) was obtained.
４−（メチルスルホニル）−２−ニトロフェノールに対
する収率は７５．３％であった。The yield based on 4-(methylsulfonyl)-2-nitrophenol was 75.3%.
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 (12)
−（アルキルスルホニル）−２−アミノフェノールを製
造するにあたり、 一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中Ｒは、炭素数１〜３のアルキル基を示す。）で表
わされる４−（アルキルチオ）フェノールを酸化して、 一般式（II） ▲数式、化学式、表等があります▼（II） （式中Ｒは、前記と同じである。） で表わされる４−（アルキルスルホニル）フェノールと
なしこれをニトロ化することにより、一般式（III） ▲数式、化学式、表等があります▼（III） （式中Ｒは、前記と同じである。） で表わされる４−（アルキルスルホニル）−２−ニトロ
フェノールとし、さらに還元することを特徴とする 一般式（IV） ▲数式、化学式、表等があります▼（IV） （式中Ｒは、前記と同じである。） で表わされる４−（アルキルスルホニル）−２−アミノ
フェノールの製造法。(1) Using 4-(alkylthio)phenol as a raw material, 4
In producing -(alkylsulfonyl)-2-aminophenol, general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, R represents an alkyl group having 1 to 3 carbon atoms. ) is oxidized to form 4-(alkylthio)phenol represented by general formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R is the same as above.) 4 -(alkylsulfonyl)phenol By nitration of this, the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R is the same as above.) General formula (IV) characterized by further reduction of 4-(alkylsulfonyl)-2-nitrophenol ▲There are numerical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R is the same as above. .) A method for producing 4-(alkylsulfonyl)-2-aminophenol represented by:
チオフェノールをハロゲン化、加水分解により製造した
ものである特許請求の範囲第１項記載の方法。(2) The method according to claim 1, wherein the 4-(alkylthio)phenol is produced by halogenating and hydrolyzing S-alkylthiophenol.
Ｓ−アルキル化により製造したものである特許請求の範
囲第１項記載の方法。(3) The method according to claim 1, wherein the 4-(alkylthio)phenol is produced by S-alkylation of phenol.
過酸化水素水を用いる特許請求の範囲第１項記載の方法
。(4) The method according to claim 1, in which aqueous hydrogen peroxide is used during the oxidation reaction of 4-(alkylthio)phenol.
いる特許請求の範囲第４項記載の方法。(5) The method according to claim 4, in which a tungstate salt is used as a catalyst during the oxidation reaction.
ある特許請求の範囲第５項記載の方法。(6) The method according to claim 5, wherein the tungstate is sodium tungstate.
化反応に硝酸を用いる特許請求の範囲第１項記載の方法
。(7) The method according to claim 1, in which nitric acid is used in the nitration reaction of 4-(alkylsulfonyl)phenol.
溶液を用いる特許請求の範囲第１項記載の方法。(8) The method according to claim 1, in which a 70-100% sulfuric acid aqueous solution is used as the nitration reaction solvent.
ールの還元反応をパラジウム触媒を用いて水添する特許
請求の範囲第１項記載の方法。(9) The method according to claim 1, wherein the reduction reaction of 4-(alkylsulfonyl)-2-nitrophenol is hydrogenated using a palladium catalyst.
る特許請求の範囲第９項記載の方法。(10) The method according to claim 9, in which palladium on carbon is used as the palladium catalyst.
特許請求の範囲第１項記載の方法。(11) The method according to claim 1, in which a lower alcohol is used as the reduction reaction solvent.
特許請求の範囲第１１項記載の方法。(12) The method according to claim 11, wherein the lower alcohol is iso-propanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62307812A JPH01149762A (en) | 1987-12-04 | 1987-12-04 | Production of 4-(alkylsulfonyl)-2-aminophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62307812A JPH01149762A (en) | 1987-12-04 | 1987-12-04 | Production of 4-(alkylsulfonyl)-2-aminophenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01149762A true JPH01149762A (en) | 1989-06-12 |
Family
ID=17973513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62307812A Pending JPH01149762A (en) | 1987-12-04 | 1987-12-04 | Production of 4-(alkylsulfonyl)-2-aminophenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01149762A (en) |
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| KR100830421B1 (en) * | 2007-03-09 | 2008-05-22 | 오영산업 주식회사 | Reactive dyes for polyamide fiber and its manufacturing method |
| CN105566182A (en) * | 2016-02-24 | 2016-05-11 | 苏州天马精细化学品股份有限公司 | Synthetic method of 2-amino-4-(ethylsulfonyl) phenol |
| WO2016194929A1 (en) * | 2015-06-04 | 2016-12-08 | 住友化学株式会社 | Method for producing perfluoroalkanesulfonyl phenol compounds |
| CN108349884A (en) * | 2015-10-30 | 2018-07-31 | 住友化学株式会社 | The manufacturing method of 2- amino -4- fortified phenols |
-
1987
- 1987-12-04 JP JP62307812A patent/JPH01149762A/en active Pending
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|---|---|---|---|---|
| WO2007077961A2 (en) * | 2005-12-28 | 2007-07-12 | Takeda Pharmaceutical Company Limited | Fused heterocyclic compounds and their use as mineralocorticoid receptor ligands |
| WO2007077961A3 (en) * | 2005-12-28 | 2007-11-22 | Takeda Pharmaceutical | Fused heterocyclic compounds and their use as mineralocorticoid receptor ligands |
| KR100830421B1 (en) * | 2007-03-09 | 2008-05-22 | 오영산업 주식회사 | Reactive dyes for polyamide fiber and its manufacturing method |
| WO2016194929A1 (en) * | 2015-06-04 | 2016-12-08 | 住友化学株式会社 | Method for producing perfluoroalkanesulfonyl phenol compounds |
| US10160722B2 (en) | 2015-06-04 | 2018-12-25 | Sumitomo Chemical Company, Limited | Method for producing perfluoroalkanesulfonyl phenol compounds |
| CN108349884A (en) * | 2015-10-30 | 2018-07-31 | 住友化学株式会社 | The manufacturing method of 2- amino -4- fortified phenols |
| EP3369726A4 (en) * | 2015-10-30 | 2019-04-17 | Sumitomo Chemical Company, Limited | Method for producing 2-amino-4-substituted phenol |
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