CN102766076A - Synthesis process of racemic phenyl ethanesulfonic acid - Google Patents
Synthesis process of racemic phenyl ethanesulfonic acid Download PDFInfo
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- CN102766076A CN102766076A CN2012102520533A CN201210252053A CN102766076A CN 102766076 A CN102766076 A CN 102766076A CN 2012102520533 A CN2012102520533 A CN 2012102520533A CN 201210252053 A CN201210252053 A CN 201210252053A CN 102766076 A CN102766076 A CN 102766076A
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- ethyl sulfonic
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- benzene ethyl
- sulfonic acid
- ethanesulfonic acid
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Abstract
The invention relates to a synthesis process of racemic phenyl ethanesulfonic acid. The conventional main production process is that 1-bromobenzene ethane is taken as a raw material to react with anhydrous ammonium hydrogen sulfite so as to generate the racemic phenyl ethanesulfonic acid, but the price of the 1-bromobenzene ethane needed by the process is high, the reaction yield is low and three wastes are multiple. The synthesis process disclosed by the invention is characterized by comprising the following steps of: reacting 1mol of styrene, 1mol of HCl water solution and 1mol of thiourea for 3-8 hours under an effect of a phase transfer catalyst quaternary ammonium salt; carrying out neutralizing by utilizing 1mol of inorganic alkali water solution to enable pH to be 5-8, reducing the temperature and separating liquid; oxidizing an organic phase in an organic acid by utilizing 2mol of hydrogen peroxide; after the oxidization, evaporating and removing the organic acid and impurities to obtain a racemic phenyl ethanesulfonic acid solution; and adding methanol to remove the salt and evaporating to obtain the racemic phenyl ethanesulfonic acid. The synthesis process disclosed by the invention selects the cheap styrene and thiourea as starting materials; sulfydryl is firstly introduced and then a target product (racemic phenyl ethanesulfonic acid) is prepared by the oxidization; and the synthesis process has the advantages of being cheap and easily-obtained in raw materials, moderate in reaction conditions, easy to control and high in yield.
Description
Technical field
The present invention relates to a kind of synthesis technique of important resolving agent, specifically is a kind of synthesis technique of DL benzene ethyl sulfonic acid.
Background technology
DL benzene ethyl sulfonic acid is as the most effective resolving agent of D-pHPG, and its Study on Preparation receives much concern.The production technique that mainly contains at present is to be raw material with the 1-bromine ethylbenzene, generates DL benzene ethyl sulfonic acid with anhydrous sodium hydrogen sulfate ammonia react.The required 1-bromine ethylbenzene of this route costs an arm and a leg, and reaction yield is low, and the three wastes are many.
Summary of the invention
The present invention is directed to the defective that prior art exists, a kind of synthesis technique of DL benzene ethyl sulfonic acid is provided, material cost is low, the source is wide, and reaction conditions is gentle, is easy to control, and yield is high.
For this reason, the present invention takes following technical scheme: a kind of synthesis technique of DL benzene ethyl sulfonic acid is characterized in that the vinylbenzene with 1mol; The 1molHCl aqueous solution and 1mol thiocarbamide are under the effect of phase-transfer catalyst quaternary ammonium salt; Reaction times 3-8 hour, use the inorganic base aqueous solution of 1mol to be neutralized to PH and be 5-8, the cooling separatory; Organic phase is used the 2mol hydrogen peroxide oxidation in organic acid; Steam after oxidation is accomplished and remove organic acid, promptly get DL benzene ethyl sulfonic acid solution behind the impurity, add the methyl alcohol desalination; Evaporate to dryness gets DL benzene ethyl sulfonic acid, and reaction equation is following:
Described quaternary ammonium salt comprises benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate.
Described quaternary ammonium salt is preferably Tetrabutyl amonium bromide.
The described reaction times is 5 hours.
The preferred aqueous sodium hydroxide solution of described inorganic base aqueous solution, the preferred value PH of neutralization reaction are 7.
Described organic acid is formic acid, glacial acetic acid.
It is starting raw material that the present invention chooses cheap vinylbenzene, thiocarbamide, introduces sulfydryl earlier, prepares title product DL benzene ethyl sulfonic acid with rear oxidation, and starting material are cheap and easy to get, and reaction conditions is gentle, is easy to control, and yield is high.
Embodiment
Below in conjunction with embodiment the present invention is further described, but protection scope of the present invention is not limited to the expression scope of embodiment.
A kind of reaction equation of synthesis technique of DL benzene ethyl sulfonic acid is following:
(±)-PES is a DL benzene ethyl sulfonic acid in the following formula,
Technical process is following:
With 1mol vinylbenzene, the 1molHCl aqueous solution and 1mol thiocarbamide are under the effect of phase-transfer catalyst quaternary ammonium salt (including but not limited to benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, preferred Tetrabutyl amonium bromide); Reaction 3-8h (preferred 5 hours) is with the inorganic base aqueous solution (including but not limited to aqueous sodium hydroxide solution, ammoniacal liquor, potassium hydroxide aqueous solution etc., preferred aqueous sodium hydroxide solution) of 1mol; Being neutralized to PH is 5-8 (preferred PH is 7), and the cooling separatory is used the 2mol hydrogen peroxide oxidation organic phase (includes but not limited to formic acid, glacial acetic acid) in organic acid in; Steam after oxidation is accomplished and remove organic acid; Promptly get α-benzene ethyl sulfonic acid solution behind the impurity, add the methyl alcohol desalination, evaporate to dryness gets α-benzene ethyl sulfonic acid; Liquid phase purity is 98%, and total recovery is 50%.
It is starting raw material that the present invention chooses cheap vinylbenzene, thiocarbamide, introduces sulfydryl earlier, prepares title product DL benzene ethyl sulfonic acid with rear oxidation, and starting material are cheap and easy to get, and reaction conditions is gentle, is easy to control, and yield is high.
What need particularly point out is; The mode of the foregoing description only limits to describe embodiment; But the present invention is confined to aforesaid way incessantly; And those skilled in the art can modify in not departing from the scope of the present invention in view of the above easily, and therefore scope of the present invention should comprise the disclosed principle and the maximum range of new feature.
Claims (6)
1. the synthesis technique of a DL benzene ethyl sulfonic acid is characterized in that the vinylbenzene with 1mol, and the 1molHCl aqueous solution and 1mol thiocarbamide are under the effect of phase-transfer catalyst quaternary ammonium salt; Reaction times 3-8 hour, use the inorganic base aqueous solution of 1mol to be neutralized to PH and be 5-8, the cooling separatory; Organic phase is used the 2mol hydrogen peroxide oxidation in organic acid, steam after oxidation is accomplished and remove organic acid, promptly gets DL benzene ethyl sulfonic acid solution behind the impurity; Add the methyl alcohol desalination, evaporate to dryness gets DL benzene ethyl sulfonic acid.
2. the synthesis technique of a kind of DL benzene ethyl sulfonic acid according to claim 1 is characterized in that described quaternary ammonium salt comprises benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate.
3. the synthesis technique of a kind of DL benzene ethyl sulfonic acid according to claim 1 is characterized in that described quaternary ammonium salt is preferably Tetrabutyl amonium bromide.
4. according to the synthesis technique of claim 2 or 3 described a kind of DL benzene ethyl sulfonic acids, it is characterized in that the described reaction times is 5 hours.
5. the synthesis technique of a kind of DL benzene ethyl sulfonic acid according to claim 4 is characterized in that the preferred aqueous sodium hydroxide solution of described inorganic base aqueous solution, and the preferred value PH of neutralization reaction is 7.
6. the synthesis technique of a kind of DL benzene ethyl sulfonic acid according to claim 5 is characterized in that described organic acid is formic acid, glacial acetic acid.
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| CN2012102520533A CN102766076A (en) | 2012-07-20 | 2012-07-20 | Synthesis process of racemic phenyl ethanesulfonic acid |
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| CN2012102520533A CN102766076A (en) | 2012-07-20 | 2012-07-20 | Synthesis process of racemic phenyl ethanesulfonic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445871A (en) * | 2017-09-07 | 2017-12-08 | 山东汉兴医药科技有限公司 | Process for producing optically active alpha-benzenesulfonic acid derivative |
| CN107721886A (en) * | 2017-10-23 | 2018-02-23 | 河南新天地药业股份有限公司 | A kind of preparation method of 1 aryl ethanesulfonic acid and its derivative |
Citations (3)
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|---|---|---|---|---|
| EP0111569A1 (en) * | 1982-06-16 | 1984-06-27 | MITSUI TOATSU CHEMICALS, Inc. | Hydroxyalkanesulfonic acids and their derivatives, and process for their preparation |
| CN101108820A (en) * | 2007-08-03 | 2008-01-23 | 浙江普洛医药科技有限公司 | Isothiuronium salt and method of manufacturing the same and method for manufacturing substituted benzene ethyl mercaptan compounds |
| CN102516133A (en) * | 2011-12-01 | 2012-06-27 | 浙江普洛医药科技有限公司 | Preparation method of methanesulfonic acid derivative |
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2012
- 2012-07-20 CN CN2012102520533A patent/CN102766076A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0111569A1 (en) * | 1982-06-16 | 1984-06-27 | MITSUI TOATSU CHEMICALS, Inc. | Hydroxyalkanesulfonic acids and their derivatives, and process for their preparation |
| CN101108820A (en) * | 2007-08-03 | 2008-01-23 | 浙江普洛医药科技有限公司 | Isothiuronium salt and method of manufacturing the same and method for manufacturing substituted benzene ethyl mercaptan compounds |
| CN102516133A (en) * | 2011-12-01 | 2012-06-27 | 浙江普洛医药科技有限公司 | Preparation method of methanesulfonic acid derivative |
Non-Patent Citations (1)
| Title |
|---|
| RICHARD M.KELLOGG 等: "Dutch Resolution: Separation of Enantiomers with Families of Resolving Agents. A Status Report", 《SYNTHESIS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445871A (en) * | 2017-09-07 | 2017-12-08 | 山东汉兴医药科技有限公司 | Process for producing optically active alpha-benzenesulfonic acid derivative |
| CN107445871B (en) * | 2017-09-07 | 2020-04-14 | 山东汉兴医药科技有限公司 | Preparation method of α -benezenesulfonic acid derivative with optical activity |
| CN107721886A (en) * | 2017-10-23 | 2018-02-23 | 河南新天地药业股份有限公司 | A kind of preparation method of 1 aryl ethanesulfonic acid and its derivative |
| CN107721886B (en) * | 2017-10-23 | 2020-11-03 | 河南新天地药业股份有限公司 | Preparation method of 1-aryl ethanesulfonic acid and derivatives thereof |
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Application publication date: 20121107 |