CN103508927A - Method for preparing 2-methanesulfonyl amino diphenyl ether - Google Patents
Method for preparing 2-methanesulfonyl amino diphenyl ether Download PDFInfo
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- CN103508927A CN103508927A CN201210209442.8A CN201210209442A CN103508927A CN 103508927 A CN103508927 A CN 103508927A CN 201210209442 A CN201210209442 A CN 201210209442A CN 103508927 A CN103508927 A CN 103508927A
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Abstract
The invention provides a method for preparing 2-methanesulfonyl amino diphenyl ether. The method comprises the following steps: at the temperature of 0-10 DEG C, dropwise adding a methane sulfonic anhydride solution to a pyridine solution containing o-amino-diphenyl ether, wherein the molar ratio of o-amino-diphenyl ether to methane sulfonic anhydride is 1:1-2, and the dropwise adding time is 0.5-1 h; and then continuing carrying out the reaction for 2-8 h to obtain 2-methanesulfonyl amino diphenyl ether. The preparation method provided by the invention has the advantages of mild reaction, simple operation, safety, high yield of 2-methanesulfonyl amino diphenyl ether, and low pollution, and is suitable for industrialized production.
Description
Technical field
The preparation method who the present invention relates to a kind of 2-methanesulfonamido phenyl ether, belongs to chemical field.
Background technology
At present, the preparation method that 2-methanesulfonamido phenyl ether is conventional is: in three mouthfuls of reaction flasks, add o-amino-diphenylethers and pyridine, be heated to 75 ℃, drip methane sulfonyl chloride, control temperature at 85 ~ 90 ℃, continue reaction 24 hours, finally reaction solution is poured in 18% hydrochloric acid (being prepared by the volume ratio of 1:1 by concentrated hydrochloric acid and water), stirring and crystallizing, filters, and makes 2-methanesulfonamido phenyl ether.But the main drawback of the method is that toxicity is high, length consuming time and the three wastes are difficult to processing etc.
Summary of the invention
Therefore, the object of this invention is to provide a kind of preparation method of 2-methanesulfonamido phenyl ether, the method, reaction temperature and, simple to operate, safety, yield is high, low pollution, is suitable for suitability for industrialized production.
The object of the invention is to be achieved through the following technical solutions.
The invention provides a kind of preparation method of 2-methanesulfonamido phenyl ether, the method comprises the following steps: at 0 ~ 10 ℃, in the pyridine solution of o-amino-diphenylethers, drip methanesulfonic anhydride solution, wherein, the mol ratio of o-amino-diphenylethers and methanesulfonic acid anhydride is 1:1 ~ 2, and time for adding is 0.5 ~ 1 hour; Then continue reaction 2 ~ 8 hours, make 2-methanesulfonamido phenyl ether.
According to preparation method provided by the invention, wherein, the solvent of described methanesulfonic anhydride solution is selected from one or more in ethylene dichloride, chloroform and methylene dichloride.
Preferably, the dichloromethane solution that described methanesulfonic anhydride solution is methanesulfonic acid anhydride.
According to preparation method provided by the invention, wherein, the concentration of described methanesulfonic anhydride solution is 1.80 ~ 1.85mol/L.
According to preparation method provided by the invention, wherein, in the pyridine solution of described o-amino-diphenylethers, the mol ratio of o-amino-diphenylethers and pyridine is 1:1 ~ 6.
According to preparation method provided by the invention, wherein, drip in the process of methanesulfonic anhydride solution, the temperature of reaction system is controlled at 0 ~ 5 ℃.
According to preparation method provided by the invention, wherein, said method comprising the steps of:
(1) in the reaction vessel with persevering stirring, pressure dropping funnel and reflux exchanger, add o-amino-diphenylethers and pyridine, wherein, the mol ratio of o-amino-diphenylethers and pyridine is 1:1 ~ 6;
(2) under agitation condition, at 0 ~ 5 ℃ of temperature, in reaction vessel, drip the dichloromethane solution that concentration is the methanesulfonic acid anhydride of 1.80 ~ 1.85mol/L, time for adding is 0.5 ~ 1 hour, then at 0 ~ 10 ℃ of temperature, react 2 ~ 8 hours, make 2-methanesulfonamido phenyl ether.
Preferably, the present invention adopts ice bath mode to control the temperature of reaction system.
According to preparation method provided by the invention, wherein, described method also comprises step (3): the reaction solution that step (2) is made is poured in hydrochloric acid, through stirring and crystallizing, filtration, obtains filter cake, by filter cake washing, dry, makes 2-methanesulfonamido phenyl ether.
Reaction formula of the present invention is as follows:
Wherein, formula (I) is o-amino-diphenylethers, and formula (II) is 2-methanesulfonamido phenyl ether.
Preparation method provided by the invention, reaction temperature and, simple to operate, safety, the yield of 2-methanesulfonamido phenyl ether is high, pollutes lowly, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, the embodiment providing is only in order to illustrate the present invention, rather than in order to limit the scope of the invention.
embodiment 1
(1) to adding 185.2g(in the reaction flask with stirring, constant pressure funnel and reflux exchanger, be 1.0mol) o-amino-diphenylethers and 316g(be 4.0mol) pyridine, open and stir, under ice bath, be cooled to 0 ℃;
(2) getting a beaker is 1.1mol by 191.6g() methanesulfonic acid anhydride is dissolved in 600ml methylene dichloride, then joined in constant pressure funnel, start to drip, keeping temperature is 0 ~ 5 ℃, in 0.5 ~ 1 hour, drip off, then 10 ℃ of following insulation reaction 4 hours;
(3) after reaction finishes, 800 milliliters of temperature of reaction solution impouring that step (2) is made are in 18% hydrochloric acid of 0 ~ 5 ℃, filter, and wash filter cake with water, make the 2-methanesulfonamido phenyl ether of 237.0g after dry, and yield is 90%, and fusing point mp is 118 ~ 120 ℃.
Adopt hydrogen nuclear magnetic resonance spectroscopy (H
1-NMR) sample is analyzed, wherein, solvent is deuterated dimethyl sulfoxide (DMSO-D6), and spectrum elucidation is as follows:
SO
2-CH
3：δ2.962ppm,S,3H；
Ar-H：δ6.858~7.440ppm,m,9H；
NH：δ9.310ppm,S,1H 。
Above-mentioned analysis further proves, the product that embodiment 1 makes is 2-methanesulfonamido phenyl ether.
embodiment 2
(1) to adding 185.2g(in the reaction flask with stirring, constant pressure funnel and reflux exchanger, be 1.0mol) o-amino-diphenylethers and 79.1g(be 1.0mol) pyridine, open and stir, under ice bath, be cooled to 0 ℃;
(2) getting a beaker is 2mol by 348.4g() methanesulfonic acid anhydride is dissolved in 1100ml methylene dichloride, then joined in constant pressure funnel, start to drip, keeping temperature is 0 ~ 5 ℃, in 0.5 ~ 1 hour, drip off, then 10 ℃ of following insulation reaction 6 hours;
(3) after reaction finishes, 800 milliliters of temperature of reaction solution impouring that step (2) is made are in 18% hydrochloric acid of 0 ~ 5 ℃, filter, and wash filter cake with water, make the 2-methanesulfonamido phenyl ether of 219g after dry, and yield is 83.3%, and fusing point mp is 117 ~ 120 ℃.
Adopt hydrogen nuclear magnetic resonance spectroscopy (H
1-NMR) sample is analyzed, wherein, solvent is deuterated dimethyl sulfoxide (DMSO-D6), and spectrum elucidation is as follows:
SO
2-CH
3：δ2.962ppm,S,3H；
Ar-H：δ6.858~7.440ppm,m,9H；
NH：δ9.310ppm,S,1H 。
Above-mentioned analysis further proves, the product that embodiment 2 makes is 2-methanesulfonamido phenyl ether.
embodiment 3
(1) to adding 185.2g(in the reaction flask with stirring, constant pressure funnel and reflux exchanger, be 1.0mol) o-amino-diphenylethers and 474.6g(be 6.0mol) pyridine, open and stir, under ice bath, be cooled to 0 ℃;
(2) getting a beaker is 1.1mol by 191.6g() methanesulfonic acid anhydride is dissolved in 600ml methylene dichloride, then joined in constant pressure funnel, start to drip, keeping temperature is 0 ~ 5 ℃, in 0.5 ~ 1 hour, drip off, then insulation reaction 8 hours at 10 ℃;
(3) after reaction finishes, the 800 milliliters of temperature of liquid impouring of answering that contragradience rapid (2) is made are, in 18% hydrochloric acid of 0 ~ 5 ℃, to filter, and wash filter cake with water, make the 2-methanesulfonamido phenyl ether of 234.9g after dry, and yield is 89.3%, and fusing point mp is 118 ~ 120 ℃.
Adopt hydrogen nuclear magnetic resonance spectroscopy (H
1-NMR) sample is analyzed, wherein, solvent is deuterated dimethyl sulfoxide (DMSO-D6), and spectrum elucidation is as follows:
SO
2-CH
3：δ2.962ppm,S,3H；
Ar-H：δ6.858~7.440ppm,m,9H；
NH：δ9.310ppm,S,1H。
Above-mentioned analysis further proves, the product that embodiment 1 makes is 2-methanesulfonamido phenyl ether.
Claims (7)
1. the preparation method of a 2-methanesulfonamido phenyl ether, the method comprises the following steps: at 0 ~ 10 ℃, drip methanesulfonic anhydride solution, wherein in the pyridine solution of o-amino-diphenylethers, the mol ratio of o-amino-diphenylethers and methanesulfonic acid anhydride is 1:1 ~ 2, and time for adding is 0.5 ~ 1 hour; Then continue reaction 2 ~ 8 hours, make 2-methanesulfonamido phenyl ether.
2. preparation method according to claim 1, wherein, the solvent of described methanesulfonic anhydride solution is selected from one or more in ethylene dichloride, chloroform and methylene dichloride;
Preferably, the dichloromethane solution that described methanesulfonic anhydride solution is methanesulfonic acid anhydride.
3. preparation method according to claim 1 and 2, wherein, the concentration of described methanesulfonic anhydride solution is 1.80 ~ 1.85mol/L.
4. according to the preparation method described in any one in claims 1 to 3, wherein, in the pyridine solution of described o-amino-diphenylethers, the mol ratio of o-amino-diphenylethers and pyridine is 1:1 ~ 6.
5. according to the preparation method described in any one in claim 1 to 4, wherein, drip in the process of methanesulfonic anhydride solution, the temperature of reaction system is controlled at 0 ~ 5 ℃.
6. according to the preparation method described in any one in claim 1 to 5, wherein, said method comprising the steps of:
(1) in the reaction vessel with stirring, constant pressure funnel and reflux exchanger, add o-amino-diphenylethers and pyridine, wherein, the mol ratio of o-amino-diphenylethers and pyridine is 1:1 ~ 6;
(2) under agitation condition, at 0 ~ 5 ℃ of temperature, in reaction vessel, drip the dichloromethane solution that concentration is the methanesulfonic acid anhydride of 1.80 ~ 1.85mol/L, time for adding is 0.5 ~ 1 hour, then at 0 ~ 10 ℃ of temperature, react 2 ~ 8 hours, make 2-methanesulfonamido phenyl ether.
7. preparation method according to claim 6, wherein, described method also comprises step (3): the reaction solution that step (2) is made is poured in hydrochloric acid, through stirring and crystallizing, filtration, obtains filter cake, by filter cake washing, dry, make 2-methanesulfonamido phenyl ether.
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| CN201210209442.8A CN103508927A (en) | 2012-06-25 | 2012-06-25 | Method for preparing 2-methanesulfonyl amino diphenyl ether |
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| CN201210209442.8A CN103508927A (en) | 2012-06-25 | 2012-06-25 | Method for preparing 2-methanesulfonyl amino diphenyl ether |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115667212A (en) * | 2020-05-29 | 2023-01-31 | 富士胶片富山化学株式会社 | High-purity N- (5-methoxy-2-phenoxyphenyl) methanesulfonamide and process for producing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1852896A (en) * | 2003-07-18 | 2006-10-25 | 葛兰素集团有限公司 | Quinoline and quinazoline derivatives having affinity for 5HT1-type receptors |
| CN101260069A (en) * | 2007-03-07 | 2008-09-10 | 天津药物研究院药业有限责任公司 | Method for preparing nimesulide intermediate 2-phenoxymethanesulphonylaniline |
-
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- 2012-06-25 CN CN201210209442.8A patent/CN103508927A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1852896A (en) * | 2003-07-18 | 2006-10-25 | 葛兰素集团有限公司 | Quinoline and quinazoline derivatives having affinity for 5HT1-type receptors |
| CN101260069A (en) * | 2007-03-07 | 2008-09-10 | 天津药物研究院药业有限责任公司 | Method for preparing nimesulide intermediate 2-phenoxymethanesulphonylaniline |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115667212A (en) * | 2020-05-29 | 2023-01-31 | 富士胶片富山化学株式会社 | High-purity N- (5-methoxy-2-phenoxyphenyl) methanesulfonamide and process for producing the same |
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