CN103880715A - Method for continuously preparing ethyl trifluoromethanesulfonate - Google Patents
Method for continuously preparing ethyl trifluoromethanesulfonate Download PDFInfo
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- CN103880715A CN103880715A CN201210552218.9A CN201210552218A CN103880715A CN 103880715 A CN103880715 A CN 103880715A CN 201210552218 A CN201210552218 A CN 201210552218A CN 103880715 A CN103880715 A CN 103880715A
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- trifluoromethanesulfonic acid
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Abstract
A disclosed method for continuously preparing ethyl trifluoromethanesulfonate comprises the following steps: (1) adding trifluoromethanesulfonic acid and diethyl sulfate with the molar ratio of (1-2):1 into a reaction kettle, switching on a stirring apparatus, raising the temperature of the reaction kettle to 50-100 DEG C, and keeping the temperature for reacting for 2-6 h; and (2) raising the temperature of the reaction kettle to 100-150 DEG C, switching on a rectifying apparatus, controlling the reflux ratio of the rectifying apparatus at (1-3):(3-1), continuously introducing trifluoromethanesulfonic acid and diethyl sulfate into the reaction kettle, controlling the speed of trifluoromethanesulfonic acid introduced into the reaction kettle at 30-70 g/min, controlling the speed of diethyl sulfate introduced into the reaction kettle at 10-50 g/min, and collecting a distillation fraction and condensing to obtain ethyl trifluoromethanesulfonate. The preparation method is short in production period and low in energy consumption, and prepared ethyl trifluoromethanesulfonate has the purity larger than 99%, the yield is 90% or more, and industrialized production can be realized.
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.
At present the synthesis technique of trifluoromethanesulfonic acid ethyl ester is mainly with ethanol or ether and trifluoromethanesulfonic acid reaction, obtains the mixture of trifluoromethanesulfonic acid second fat and water, then through separatory, the postprocessing working procedures such as dry.
The shortcoming that above-mentioned synthesis technique exists is: the production cycle is long, energy consumption is high, side reaction is many, can generate the by product such as ethene, a hydration trifluoromethanesulfonic acid, and 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, preparation product purity and all methods of higher a kind of continuous production trifluoromethanesulfonic acid ethyl ester of yield.
For achieving the above object, the present invention has adopted following technical scheme.
A kind of method of continuous production trifluoromethanesulfonic acid ethyl ester, comprise the following steps: (1) in reactor, add trifluoromethanesulfonic acid and ethyl sulfate, 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, the speed that control trifluoromethanesulfonic acid passes in reactor is 30~70g/min, and the speed that control ethyl sulfate passes in reactor is 10~50g/min; Collect fraction condensation and obtain 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 from reactor bottom, obtains technical grade sulfuric acid after by product sulfuric acid treatment.
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 be realized 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, in reactor, add continuously trifluoromethanesulfonic acid and ethyl sulfate, 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, 115 ± 3 DEG C of left and right, is collected fraction 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%.
Produce after certain hour, can regularly discharge by product sulfuric acid from reactor bottom, after by product sulfuric acid treatment, can be used as technical grade sulfuric acid 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, in reactor, add continuously trifluoromethanesulfonic acid and ethyl sulfate, 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, 115 ± 3 DEG C of left and right, is collected fraction 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%.
Produce after certain hour, can regularly discharge by product sulfuric acid from reactor bottom, after by product sulfuric acid treatment, can be used as technical grade sulfuric acid 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, in reactor, add continuously trifluoromethanesulfonic acid and ethyl sulfate, 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, 115 ± 3 DEG C of left and right, is collected fraction 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%.
Produce after certain hour, can regularly discharge by product sulfuric acid from reactor bottom, after by product sulfuric acid treatment, can be used as technical grade sulfuric acid 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, in reactor, add continuously trifluoromethanesulfonic acid and ethyl sulfate, 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, 115 ± 3 DEG C of left and right, is collected fraction 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 3 Kg altogether, and ethyl sulfate 1.54 Kg, receive product trifluoromethanesulfonic acid ethyl ester 3.26Kg, yield 90.7%.
Produce after certain hour, can regularly discharge by product sulfuric acid from reactor bottom, after by product sulfuric acid treatment, can be used as technical grade sulfuric acid 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) in reactor, add trifluoromethanesulfonic acid and ethyl sulfate, 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, the speed that control trifluoromethanesulfonic acid passes in reactor is 30~70g/min, and the speed that control ethyl sulfate passes in reactor is 10~50g/min; Collect fraction condensation and obtain 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 discharge by product sulfuric acid from reactor bottom, obtain technical grade sulfuric acid after by product sulfuric acid treatment.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106008282A (en) * | 2016-05-27 | 2016-10-12 | 中国科学院上海有机化学研究所 | Method for synthesizing trifluoromethanesulfonate |
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 |
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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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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 |
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BOOTH, BRIAN L ET AL: "Alkyltrifluoromethanesulfonates as alkylating reagents for aromatic compounds", 《JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS I:ORGANIC AND BIO-ORGANIC CHEMISTRY》, no. 12, 31 December 1980 (1980-12-31), XP002249731, DOI: doi:10.1039/p19800002887 * |
FORBUS, T. R ET AL: "Reactions of the readily accessible electrophile, trifluoroacetyl triflate: a very reactive agent for trifluoroacetylations at oxygen, nitrogen, carbon, or halogen centers", 《JOURNAL OF ORGANIC CHEMISTRY》, vol. 52, no. 19, 31 December 1987 (1987-12-31) * |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106008282A (en) * | 2016-05-27 | 2016-10-12 | 中国科学院上海有机化学研究所 | Method for synthesizing trifluoromethanesulfonate |
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 |
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