JPS5899451A - Preparation of p-acetamidothymol - Google Patents
Preparation of p-acetamidothymolInfo
- Publication number
- JPS5899451A JPS5899451A JP19771081A JP19771081A JPS5899451A JP S5899451 A JPS5899451 A JP S5899451A JP 19771081 A JP19771081 A JP 19771081A JP 19771081 A JP19771081 A JP 19771081A JP S5899451 A JPS5899451 A JP S5899451A
- Authority
- JP
- Japan
- Prior art keywords
- acetamidothymol
- preparation
- iron
- tin
- zinc
- 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
- 238000002360 preparation method Methods 0.000 title claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000005844 Thymol Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229960000790 thymol Drugs 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- VRYMTAVOXVTQEF-UHFFFAOYSA-N acetic acid [4-[2-(dimethylamino)ethoxy]-2-methyl-5-propan-2-ylphenyl] ester Chemical compound CC(C)C1=CC(OC(C)=O)=C(C)C=C1OCCN(C)C VRYMTAVOXVTQEF-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 1
- 229960003509 moxisylyte Drugs 0.000 description 1
- XEUGNUKPMRRHMD-UHFFFAOYSA-N n-(2-hydroxy-6-methyl-3-propan-2-ylphenyl)acetamide Chemical compound CC(C)C1=CC=C(C)C(NC(C)=O)=C1O XEUGNUKPMRRHMD-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は下記式（１）
を有するアセトアミドチモール（１−メチル−３−ヒド
ロキシ−４−イソゾロビル−６一アセトアミドベンゼン
）の製法に関し、下記式Ｑ［）を有するチモールを、鉄
、亜鉛またはスズの存在の−とで、無水酢酸および亜硝
酸と反応せしめてチモールに７セトアミド基を導入する
ことからなる上記ｐ−ア七ドアｉトチモールの製法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing acetamidothymol (1-methyl-3-hydroxy-4-isozorobyl-6-acetamidobenzene) having the following formula (1). , in the presence of iron, zinc or tin, the method for the preparation of p-7doi-tothymol as described above, which comprises reacting with acetic anhydride and nitrous acid to introduce a 7cetamido group into thymol.
上記ｐ−ア七トドアミドチモール、医薬品として用いら
れるチモキザミン（５−（Ｎ、Ｎ−ジメチルアミノアル
コキシ）カルノリ１−ルアセテート）またはその誘導体
管合成するための原料として用いられ、従来ｐ−アセト
アミドチモールの製法としては興国特許ＪＲ７４５，０
７０号公報、ドイツ特許ｗＪ９０５，７３８号公報なら
びにＢｕｌｌ、Ｓｏｃ。The above p-acetamidothymol is used as a raw material for synthesizing thymoxamine (5-(N,N-dimethylaminoalkoxy)carnolyl-acetate) used as a pharmaceutical or its derivatives, and conventionally p-acetamidothymol The manufacturing method is Kokoku Patent JR745,0
No. 70, German patent wJ905,738 and Bull, Soc.
Ｃｈｌｔｍ、 Ｆｒａｔ＋ｃｏ 第５巻、８３９〜８
４９ページ（１９５９）にすでに開示されているが、こ
れらの文献に記載されている方法では、いずれもチモー
ル力Ｃ）ｐ−アセトアミドチモールを得るのに３工程を
必要とし、その製造工程において多量の亜硝酸ガスを発
生するという欠点を有し、またその製法においては硫化
水軍を用いなければならないｅ従って上記文献に記載さ
れている、ｐ−ア七ドアきトチモールの製造法は、工業
的に紘すぐれた方法であるとはいえない。Chltm, Frat+co Volume 5, 839-8
49 (1959), all of the methods described in these documents require three steps to obtain thymol C) p-acetamidothymol, and a large amount of It has the disadvantage of generating nitrite gas, and the production method requires the use of sulfide water.Therefore, the method for producing p-7d totimol described in the above-mentioned document is not suitable for industrial use. It cannot be said that it is an excellent method.
本発明は、ｐ−アセトアミドチモールを工業的に製造す
ること金目的として開発されたものであって、本発明の
方法は鉄、亜鉛またはスズを触媒として用い、その存在
下において、チモールを無するものであって、その詳細
な方法を下記に実施例をもって説明する。The present invention was developed for the purpose of industrially producing p-acetamidothymol, and the method of the present invention uses iron, zinc or tin as a catalyst, and in the presence of iron, zinc or tin, thymol is eliminated. The detailed method will be explained below with reference to examples.
例
上記式（１によって示すチモール３００ｊｌ（２モル）
をアセトン４００肩ｌに溶解し、この溶液に、水
亜硝酸ナトリウム１３８ｊｌ （２モル）をイ００１１
７に保ちながら１時間かきまぜをつづけた０次いでこの
溶液に還元鉄２２０ＪＦ（３，９モル）を加え九彼、φ
に酢Ｉ１６００耐と無水酢酸６００７１（５，９モル）
を滴下して加え、６ＦＩ！ＩＰ間かきまぜ含つづけた後
、ろ過して、還元鉄を除き、ろ液に水３Ｊｔ加え、析出
した結晶をろ取し、この結晶を１．２−ジクＩルエタン
によって再結６管行表い、無色の結晶として、式（１）
で示されるｐ−アセトアミドチモール（ｍ、ｐ、 １７
２〜１７５℃）３３５ＪＩ（収率８１．〇−）を得た。Example Thymol 300jl (2 mol) shown by the above formula (1)
was dissolved in 400 liters of acetone, and 138 liters (2 mol) of sodium nitrite was added to this solution.
Stirring was continued for 1 hour while maintaining the temperature of
Vinegar I 1600 resistant and acetic anhydride 60071 (5,9 mol)
Add dropwise and add 6FI! After continuing to stir during IP, filter to remove reduced iron, add 3 Jt of water to the filtrate, collect the precipitated crystals by filtration, and reconstitute the crystals with 1,2-dichloroethane in 6 tubes. , as a colorless crystal, formula (1)
p-acetamidothymol (m, p, 17
2-175°C) 335JI (yield 81.0-) was obtained.
上記例において用い友亜硝酸ナトリウムの代〉に、亜硝
酸イソアミルを用いた以外は、上記例の方法と同じ方法
によりて、目的とするｐ−アセトアミドチモールを収率
８５．２チで得た。The target p-acetamidothymol was obtained in a yield of 85.2% by the same method as in the above example except that isoamyl nitrite was used in place of the sodium nitrite used in the above example.
また、上記例において触媒として用いた還元鉄の代りに
、鉄粉、亜鉛またはスズを用いた場合、その収率に着干
の差社あるにしても、上記と同じようにｐ−アセトアミ
ドチモールが得られることがわかった。Furthermore, if iron powder, zinc, or tin is used instead of the reduced iron used as a catalyst in the above example, p-acetamidothymol will be produced in the same way as above, even if there is a difference in yield. I found out that I can get it.
Claims (1)
式（Ｉｔ） ｔ−有するチモール會、鉄、亜鉛またはスズの存在下に
おいて、無水詐欺および亜硝酸と反応せしめることを特
徴とする上ｋｐ−アセトアミドチモールの製法。[Claims] A method for producing p-acetamidothymol having the formula (rit-t-),
A process for the preparation of kp-acetamidothymol having the formula (It) t-, which is characterized in that it is reacted with anhydride and nitrous acid in the presence of iron, zinc or tin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19771081A JPS5899451A (en) | 1981-12-10 | 1981-12-10 | Preparation of p-acetamidothymol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19771081A JPS5899451A (en) | 1981-12-10 | 1981-12-10 | Preparation of p-acetamidothymol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5899451A true JPS5899451A (en) | 1983-06-13 |
| JPS6338982B2 JPS6338982B2 (en) | 1988-08-03 |
Family
ID=16379065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19771081A Granted JPS5899451A (en) | 1981-12-10 | 1981-12-10 | Preparation of p-acetamidothymol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5899451A (en) |
-
1981
- 1981-12-10 JP JP19771081A patent/JPS5899451A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6338982B2 (en) | 1988-08-03 |
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