CN103880715B - A kind of method of continuous production trifluoromethanesulfonic acid ethyl ester - Google Patents
A kind of method of continuous production trifluoromethanesulfonic acid ethyl ester Download PDFInfo
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- CN103880715B CN103880715B CN201210552218.9A CN201210552218A CN103880715B CN 103880715 B CN103880715 B CN 103880715B CN 201210552218 A CN201210552218 A CN 201210552218A CN 103880715 B CN103880715 B CN 103880715B
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Abstract
The invention discloses a kind of method of continuous production trifluoromethanesulfonic acid ethyl ester, comprise the following steps: (1) add trifluoromethanesulfonic acid and ethyl sulfate in a kettle., the mol ratio of trifluoromethanesulfonic acid and ethyl sulfate is (1 ~ 2): 1, open whipping appts, reactor is warming up to 50 ~ 100 DEG C, insulation reaction 2 ~ 6 hours; (2) reactor is warming up to 100 ~ 150 DEG C, open rectifier unit, controlling rectifier unit reflux ratio is (1 ~ 3): (3 ~ 1), simultaneously, trifluoromethanesulfonic acid and ethyl sulfate are passed in reactor continuously, controlling the trifluoromethanesulfonic acid speed passed in reactor is 30 ~ 70g/min, and controlling the ethyl sulfate speed passed in reactor is 10 ~ 50g/min; Collect fraction condensation obtains trifluoromethanesulfonic acid ethyl ester.Above-mentioned preparation method, with short production cycle, energy consumption is low, the purity of the trifluoromethanesulfonic acid ethyl ester of preparation is greater than 99%, and yield, more than 90%, can realize suitability for industrialized production.
Description
Technical field
The present invention relates to the preparation method of trifluoromethanesulfonic acid ethyl ester.
Background technology
Trifluoromethanesulfonic acid ethyl ester is the derivative of trifluoromethanesulfonic acid, is widely used in the intermediate of the industry such as chemical industry, medicine.
The synthesis technique of current trifluoromethanesulfonic acid ethyl ester mainly with ethanol or ether and trifluoromethanesulfonic acid reaction, obtains the mixture of trifluoromethanesulfonic acid second fat and water, then through the postprocessing working procedures such as separatory, drying.
The shortcoming that above-mentioned synthesis technique exists is: the production cycle is long, energy consumption is high, side reaction is many, and can generate the by product such as ethene, a hydration trifluoromethanesulfonic acid, yield is lower.
Summary of the invention
The object of this invention is to provide a kind of technique simple, with short production cycle, energy consumption is low, the method for the product purity of preparation and all higher a kind of continuous production trifluoromethanesulfonic acid ethyl ester of yield.
For achieving the above object, present invention employs following technical scheme.
A kind of method of continuous production trifluoromethanesulfonic acid ethyl ester, comprise the following steps: (1) add trifluoromethanesulfonic acid and ethyl sulfate in a kettle., the mol ratio of trifluoromethanesulfonic acid and ethyl sulfate is (1 ~ 2): 1, open whipping appts, reactor is warming up to 50 ~ 100 DEG C, insulation reaction 2 ~ 6 hours; (2) reactor is warming up to 100 ~ 150 DEG C, open rectifier unit, controlling rectifier unit reflux ratio is (1 ~ 3): (3 ~ 1), simultaneously, trifluoromethanesulfonic acid and ethyl sulfate are passed in reactor continuously, controlling the trifluoromethanesulfonic acid speed passed in reactor is 30 ~ 70g/min, and controlling the ethyl sulfate speed passed in reactor is 10 ~ 50g/min; Collect fraction condensation obtains trifluoromethanesulfonic acid ethyl ester.
Further, the method for aforesaid a kind of continuous production trifluoromethanesulfonic acid ethyl ester, wherein, step (1) in the mol ratio of trifluoromethanesulfonic acid and ethyl sulfate be 2: 1.
Further, the method for aforesaid a kind of continuous production trifluoromethanesulfonic acid ethyl ester, wherein, regularly discharges by product sulfuric acid, obtains technical grade sulfuric acid after by product sulfuric acid treatment bottom reactor.
Beneficial effect of the present invention: preparation method's technique of the present invention is simple, with short production cycle, energy consumption is low, the purity of the trifluoromethanesulfonic acid ethyl ester of preparation is greater than 99%, and yield, more than 90%, can realize suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
embodiment 1.
(1) 300g trifluoromethanesulfonic acid and 154g ethyl sulfate are dropped in 5L glass reaction still, open and stir, then reactor is warming up to 80 DEG C, insulation reaction 5 hours; (2) reactor is warming up to 110 ~ 130 DEG C, opens rectifying tower valve, controlling reflux ratio is 1: 1; Simultaneously, trifluoromethanesulfonic acid and ethyl sulfate is added continuously in reactor, trifluoromethanesulfonic acid joins in reactor continuously with the speed of 30g/min, ethyl sulfate joins in reactor continuously with the speed of 15g/min, after reactive distillation, rectifying tower tower top temperature-stable, at about 115 ± 3 DEG C, collects fraction and condensation, in distillate, the chromatographic purity of trifluoromethanesulfonic acid ethyl ester is up to 99.3%, in product introduction finished product holding tank.This test drops into trifluoromethanesulfonic acid 3Kg altogether, and ethyl sulfate 1.54Kg, receives product trifluoromethanesulfonic acid ethyl ester 3.3Kg, yield 92.0%.
After producing certain hour, regularly can discharge by product sulfuric acid bottom reactor, can be used as technical grade sulfuric acid after by product sulfuric acid treatment and sell.
embodiment 2.
(1) 300g trifluoromethanesulfonic acid and 154g ethyl sulfate are dropped in 5L glass reaction still, open and stir, then reactor is warming up to 50 DEG C, insulation reaction 2 hours; (2) reactor is warming up to 100 ~ 120 DEG C, opens rectifying tower valve, controlling reflux ratio is 1: 1; Simultaneously, trifluoromethanesulfonic acid and ethyl sulfate is added continuously in reactor, trifluoromethanesulfonic acid joins in reactor continuously with the speed of 35g/min, ethyl sulfate joins in reactor continuously with the speed of 32g/min, after reactive distillation, rectifying tower tower top temperature-stable, at about 115 ± 3 DEG C, collects fraction and condensation, in distillate, the chromatographic purity of trifluoromethanesulfonic acid ethyl ester is up to 99.2%, in product introduction finished product holding tank.This test drops into trifluoromethanesulfonic acid 3Kg altogether, and ethyl sulfate 1.54Kg, receives product trifluoromethanesulfonic acid ethyl ester 3.28Kg, yield 91.4%.
After producing certain hour, regularly can discharge by product sulfuric acid bottom reactor, can be used as technical grade sulfuric acid after by product sulfuric acid treatment and sell.
embodiment 3.
(1) 300g trifluoromethanesulfonic acid and 154g ethyl sulfate are dropped in 5L glass reaction still, open and stir, then reactor is warming up to 60 DEG C, insulation reaction 2 hours; (2) reactor is warming up to 120 ~ 140 DEG C, opens rectifying tower valve, controlling reflux ratio is 3: 1; Simultaneously, trifluoromethanesulfonic acid and ethyl sulfate is added continuously in reactor, trifluoromethanesulfonic acid joins in reactor continuously with the speed of 30g/min, ethyl sulfate joins in reactor continuously with the speed of 15g/min, after reactive distillation, rectifying tower tower top temperature-stable, at about 115 ± 3 DEG C, collects fraction and condensation, in distillate, the chromatographic purity of trifluoromethanesulfonic acid ethyl ester is up to 99.4%, in product introduction finished product holding tank.This test drops into trifluoromethanesulfonic acid 3Kg altogether, and ethyl sulfate 1.54Kg, receives product trifluoromethanesulfonic acid ethyl ester 3.32Kg, yield 92.7%.
After producing certain hour, regularly can discharge by product sulfuric acid bottom reactor, can be used as technical grade sulfuric acid after by product sulfuric acid treatment and sell.
embodiment 4.
(1) 300g trifluoromethanesulfonic acid and 154g ethyl sulfate are dropped in 5L glass reaction still, open and stir, then reactor is warming up to 100 DEG C, insulation reaction 6 hours; (2) reactor is warming up to 140 ~ 150 DEG C, opens rectifying tower valve, controlling reflux ratio is 1: 3; Simultaneously, trifluoromethanesulfonic acid and ethyl sulfate is added continuously in reactor, trifluoromethanesulfonic acid joins in reactor continuously with the speed of 70g/min, ethyl sulfate joins in reactor continuously with the speed of 50g/min, after reactive distillation, rectifying tower tower top temperature-stable, at about 115 ± 3 DEG C, collects fraction and condensation, in distillate, the chromatographic purity of trifluoromethanesulfonic acid ethyl ester is up to 99.1%, in product introduction finished product holding tank.This test drops into trifluoromethanesulfonic acid 3Kg altogether, and ethyl sulfate 1.54Kg, receives product trifluoromethanesulfonic acid ethyl ester 3.26Kg, yield 90.7%.
After producing certain hour, regularly can discharge by product sulfuric acid bottom reactor, can be used as technical grade sulfuric acid after by product sulfuric acid treatment and sell.
Claims (3)
1. the method for a continuous production trifluoromethanesulfonic acid ethyl ester, it is characterized in that: comprise the following steps: (1) add trifluoromethanesulfonic acid and ethyl sulfate in a kettle., the mol ratio of trifluoromethanesulfonic acid and ethyl sulfate is (1 ~ 2): 1, open whipping appts, reactor is warming up to 50 ~ 100 DEG C, insulation reaction 2 ~ 6 hours; (2) reactor is warming up to 100 ~ 150 DEG C, open rectifier unit, controlling rectifier unit reflux ratio is (1 ~ 3): (3 ~ 1), simultaneously, trifluoromethanesulfonic acid and ethyl sulfate are passed in reactor continuously, controlling the trifluoromethanesulfonic acid speed passed in reactor is 30 ~ 70g/min, and controlling the ethyl sulfate speed passed in reactor is 10 ~ 50g/min; Collect fraction condensation obtains trifluoromethanesulfonic acid ethyl ester.
2. the method for a kind of continuous production trifluoromethanesulfonic acid ethyl ester according to claim 1, is characterized in that: step (1) in the mol ratio of trifluoromethanesulfonic acid and ethyl sulfate be 2: 1.
3. the method for a kind of continuous production trifluoromethanesulfonic acid ethyl ester according to claim 1 and 2, is characterized in that: regularly bottom reactor, discharge by product sulfuric acid, obtain technical grade sulfuric acid after by product sulfuric acid treatment.
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| CN103880715B true CN103880715B (en) | 2016-04-06 |
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Families Citing this family (2)
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| CN106008282B (en) * | 2016-05-27 | 2018-01-23 | 中国科学院上海有机化学研究所 | The synthetic method of trifluoromethane sulfonic acid ester |
| CN109776319A (en) * | 2019-03-27 | 2019-05-21 | 南通宝凯化工有限公司 | A kind of production technology of trifluoroacetone acetoacetic ester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772344A (en) * | 1970-10-23 | 1973-11-13 | Bayer Ag | Methanesulfonic acid esters of 4-trifluoromethylphenols |
| CN101229519A (en) * | 2003-11-18 | 2008-07-30 | 萨索尔溶剂德国股份有限公司 | Process for the production of metal salts of trifluoromethane sulphonic acid and their use as esterification catalysts |
| CN101511782A (en) * | 2006-09-12 | 2009-08-19 | 和光纯药工业株式会社 | Process for production of sulfonic acid ester |
| WO2012021409A2 (en) * | 2010-08-11 | 2012-02-16 | Utah State University | Anthraquinone Analogs |
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2012
- 2012-12-19 CN CN201210552218.9A patent/CN103880715B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772344A (en) * | 1970-10-23 | 1973-11-13 | Bayer Ag | Methanesulfonic acid esters of 4-trifluoromethylphenols |
| CN101229519A (en) * | 2003-11-18 | 2008-07-30 | 萨索尔溶剂德国股份有限公司 | Process for the production of metal salts of trifluoromethane sulphonic acid and their use as esterification catalysts |
| CN101511782A (en) * | 2006-09-12 | 2009-08-19 | 和光纯药工业株式会社 | Process for production of sulfonic acid ester |
| WO2012021409A2 (en) * | 2010-08-11 | 2012-02-16 | Utah State University | Anthraquinone Analogs |
Non-Patent Citations (5)
| Title |
|---|
| Alkyltrifluoromethanesulfonates as alkylating reagents for aromatic compounds;Booth, Brian L et al;《Journal of the Chemical Society, Perkin Transactions I：Organic and Bio-Organic Chemistry》;19801231(第12期);2887-2894 * |
| Reactions of the readily accessible electrophile, trifluoroacetyl triflate: a very reactive agent for trifluoroacetylations at oxygen, nitrogen, carbon, or halogen centers;Forbus, T. R et al;《Journal of Organic Chemistry》;19871231;第52卷(第19期);4156-4159 * |
| 三氟甲磺酸衍生物的制备及其应用;吕灵华等;《化学工程与装备》;20090430(第4期);93-97 * |
| 三氟甲磺酸衍生物的制备及其应用;吕灵华等;《船舰防化》;20091231(第5期);25-29 * |
| 吕灵华等.三氟甲基磺酸的生产工艺综述.《舰船防化》.2008,(第5期), * |
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Address after: 215600 No.35 Nanhai Road, Jiangsu Yangzijiang International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu Province Patentee after: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. Address before: Zhangjiagang Guotai Huarong chemical new material Co., Ltd., No.9 Nanhai Road, Yangzijiang International Chemical Industrial Park, Zhangjiagang City, Suzhou City, Jiangsu Province, 215633 Patentee before: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. |