CN102442929A - Method for preparing 4- (2-hydroxyethyl sulfone) acetanilide - Google Patents
Method for preparing 4- (2-hydroxyethyl sulfone) acetanilide Download PDFInfo
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- CN102442929A CN102442929A CN2011103665003A CN201110366500A CN102442929A CN 102442929 A CN102442929 A CN 102442929A CN 2011103665003 A CN2011103665003 A CN 2011103665003A CN 201110366500 A CN201110366500 A CN 201110366500A CN 102442929 A CN102442929 A CN 102442929A
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- China
- Prior art keywords
- acetanilide
- preparing
- hydroxyethyl sulfone
- kharophen
- sulfinic acid
- 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.)
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- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229960001413 acetanilide Drugs 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 title abstract description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 11
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- RWDJJOUSDATHMI-UHFFFAOYSA-N benzenesulfinic acid;sodium Chemical compound [Na].OS(=O)C1=CC=CC=C1 RWDJJOUSDATHMI-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- YDQNDKBOOVXRTL-UHFFFAOYSA-N 4-acetamidobenzenesulfinic acid Chemical compound CC(=O)NC1=CC=C(S(O)=O)C=C1 YDQNDKBOOVXRTL-UHFFFAOYSA-N 0.000 abstract 3
- 239000000047 product Substances 0.000 abstract 2
- GRDXCFKBQWDAJH-UHFFFAOYSA-N 4-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=C(S(Cl)(=O)=O)C=C1 GRDXCFKBQWDAJH-UHFFFAOYSA-N 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 235000010265 sodium sulphite Nutrition 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000007787 solid Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 4- (2-hydroxyethyl sulfone) acetanilide, which comprises the steps of controlling the temperature to be 30-35 ℃, reacting 4-acetamidobenzenesulfonyl chloride, sodium sulfite and sodium bicarbonate for 1.5-2 hours, cooling, filtering to remove salt, adding hydrochloric acid into filtrate for acidification, and filtering to obtain 4-acetamidobenzene sulfinic acid; suspending 4-acetaminophenylsulfinic acid in water, adjusting the pH value to 7.5-8, dropwise adding chloroethanol, controlling the temperature to 96-100 ℃, controlling the pH value to 7.5-8, preserving the heat for 8-10 hours, and cooling to separate out a product. The method for preparing 4- (2-hydroxyethyl sulfone) acetanilide has the following outstanding advantages: the method adopts the steps of preparing the 4-acetamido benzene sulfinic acid and then preparing the 4- (2-hydroxyethyl sulfone) acetanilide, is a two-step preparation method, has the advantages of easily obtained raw materials, simple operation, low cost, easy industrial production, high product yield of more than 90 percent, high purity of more than 99 percent (HPLC), good practicability and can generate better economic benefit and social benefit.
Description
Technical field
The invention belongs to the organic cpds synthesis technical field, be specifically related to the method for a kind of 4-of preparation (2-hydroxyethyl sulfone) Acetanilide.
Background technology
4-(2-hydroxyethyl sulfone) Acetanilide is a kind of important intermediate of reactive dyestuffs, and not seeing both at home and abroad has this compound research report.
Summary of the invention
Goal of the invention: to the deficiency that exists in the prior art, the purpose of this invention is to provide the method for a kind of 4-of preparation (2-hydroxyethyl sulfone) Acetanilide, to realize that making it have raw material is easy to get, technology is simple, and product yield is high, is convenient to advantages such as suitability for industrialized production.
Technical scheme: in order to realize the foregoing invention purpose, the technical scheme that the present invention adopts is following:
A kind of method for preparing 4-(2-hydroxyethyl sulfone) Acetanilide may further comprise the steps:
(1) in water, be raw material with the 4-ASC, with mol ratio 1:1 ~ 1.3:3 ~ 4,30 ~ 35 ℃ reaction 1.5 ~ 2h, be cooled to 10 ℃ through S-WAT and sodium bicarbonate, suction filtration filtering salinity, filtrating adds hydrochloric acid, and suction filtration gets 4-kharophen benzene sulfinic acid.Concrete reaction formula is following:
(2) 4-kharophen benzene sulfinic acid sodium is added in the glycol chlorohydrin, dropwise liquid is regulated pH7.5 ~ 8,96 ~ 100 ℃ of temperature controls, and control pH7.5 ~ 8, insulation 8 ~ 10h, product 4-(2-hydroxyethyl sulfone) Acetanilide is separated out in cooling.Concrete reaction formula is following:
The above-mentioned method for preparing 4-(2-hydroxyethyl sulfone) Acetanilide, concrete steps comprise:
(1) water, S-WAT, sodium bicarbonate are added in the reaction flask, adjust the temperature to 35 ~ 40 ℃, slowly add the 4-ASC; 30 ℃ of temperature controls, the reinforced end is cooled to 10 ℃ with material; The filtering salinity; Filtrating adds the hydrochloric acid acid out to pH1, and filtration drying gets 4-kharophen benzene sulfinic acid; Wherein, the amount ratio of 4-ASC, S-WAT, sodium bicarbonate and water is 1mol:1 ~ 1.3mol:3 ~ 5mol:600mL;
(2) with in the 4-kharophen benzene sulfinic acid sodium adding glycol chlorohydrin, dropwise liquid is regulated pH7.5 ~ 8,96 ~ 100 ℃ of temperature controls, and control pH7.5 ~ 8 keep 8 ~ 10h, are cooled to 10 ℃, filter 60 ℃ of dry 4-(2-hydroxyethyl sulfone) Acetanilide bullions that get;
(3) get 4-(2-hydroxyethyl sulfone) Acetanilide (2) elaboration with the refining bullion of 95% ethanol, 95% amount of ethanol is 9 ~ 12 times of bullion weight.
Beneficial effect: the method for 4-of the present invention (2-hydroxyethyl sulfone) Acetanilide, the outstanding advantage that has comprises: this method adopts preparation 4-kharophen benzene sulfinic acid earlier, and then preparation 4-(2-hydroxyethyl sulfone) Acetanilide, is two one step preparation methods; This method raw material is easy to get, and simple to operate, cost is low, is easy to suitability for industrialized production; Product yield is high, and greater than 90%, purity is high; Greater than 99% (HPLC), have good practicability, can produce favorable economic benefit and social benefit.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation.
Embodiment 1
In the 1000mL reaction flask, add entry 120mL, S-WAT 80.6g (0.64mol), sodium hydrogencarbonate 161.3g (1.92mol) under agitation evenly drops into 4-ASC 120g (0.64mol); Controlled temperature is below 30 ℃, and feeding intake finishes, and heats up, and makes temperature between 30 ~ 35 ℃, react 1.5h; Feed liquid becomes yellow by white, is cooled to 10 ℃, suction filtration, filtering inorganic salt; Filtrating uses 30% hydrochloric acid to transfer to pH1, and the about 150g of 30% hydrochloric acid separates out white produce article; Suction filtration, 60 ℃ of dry 4-kharophen benzene sulfinic acid 101.6g (0.51mol) that get, yield is 80.26%.
In the 250mL reaction flask, add glycol chlorohydrin 61.7g (0.77mol), add 4-kharophen benzene sulfinic acid 127.5g (0.64mol), feed liquid is muddy; Be brown, transfer pH7.5 with 20% sodium hydroxide, feed liquid is transparent, slowly is warming up to 96 ~ 100 ℃; And under this temperature, be incubated 10h, and constantly transfer pH that it is kept between 7.5 ~ 8 in the process with 20% sodium hydroxide, insulation finishes to be cooled to 10 ℃ of a large amount of white solids; Reaction finishes, and filters, dry 4-(2-hydroxyethyl sulfone) the Acetanilide bullion 124.6g that gets; Yield 80.02%, fusing point: 192 ~ 197 ℃, content is greater than 96% (HPLC).Bullion joined recrystallization gets elaboration 113.2g, yield 90.84% in 783g 95% ethanol.White crystalline solid, 197.5 ~ 198.8 ℃ of fusing points, content 99.38% (HPLC).
Embodiment 2
In the 1000mL reaction flask, add entry 120mL, S-WAT 100.8g (0.8mol), sodium hydrogencarbonate 215g (2.56mol) under agitation evenly drops into 4-ASC 120g (0.64mol); Controlled temperature is below 30 ℃, and feeding intake finishes, and heats up, and makes temperature between 30 ~ 35 ℃, react 2h; Feed liquid becomes yellow by white, is cooled to 10 ℃, suction filtration, filtering inorganic salt; Filtrating uses 30% salt acid out to pH1, and the about 170g of 30% hydrochloric acid separates out white produce article; Suction filtration, 60 ℃ of dry 4-kharophen benzene sulfinic acid 105.6g (0.53mol) that get, yield is 82.52%.
In the 250mL reaction flask, add glycol chlorohydrin 72.1g (0.9mol), add 4-kharophen benzene sulfinic acid 127.5g (0.64mol), feed liquid is muddy; Be brown, transfer pH 7.5 (7.5 ~ 8) with 20% sodium hydroxide, feed liquid is transparent, slowly is warming up to 96 ~ 100 ℃; And under this temperature, be incubated 8h, and constantly transfer pH that it is kept between 7.5 ~ 8 in the process with 20% sodium hydroxide, insulation finishes to be cooled to 10 ℃ of a large amount of white solids; Reaction finishes, and filters, dry 4-(2-hydroxyethyl sulfone) the Acetanilide bullion 122.3g that gets; Yield 78.53%, fusing point: 192 ~ 197 ℃, content is greater than 96% (HPLC).Above-mentioned bullion joins that recrystallization gets elaboration 111.8g, yield 91.44% in 783g 95% ethanol.White crystalline solid, 197.3 ~ 198.5 ℃ of fusing points, content 99.45% (HPLC).
Embodiment 3
In reaction vessel, add entry 600mL, S-WAT 1mol, sodium hydrogencarbonate 3mol under agitation evenly drops into 4-ASC 1mol; Controlled temperature is below 30 ℃, and feeding intake finishes, and heats up, and makes temperature between 30 ~ 35 ℃, react 1.5h; Feed liquid becomes yellow by white, is cooled to 10 ℃, suction filtration, filtering inorganic salt; Filtrating uses 30% hydrochloric acid to transfer to pH1, separates out white produce article, suction filtration, 60 ℃ of dry 4-kharophen benzene sulfinic acids that get.
In reaction vessel, add glycol chlorohydrin 1.2mol, add 4-kharophen benzene sulfinic acid 1mol, feed liquid is muddy; Be brown, transfer pH7.5 with 20% sodium hydroxide, feed liquid is transparent, slowly is warming up to 96 ~ 100 ℃; And under this temperature, be incubated 8h, and constantly transfer pH that it is kept between 7.5 ~ 8 in the process with 20% sodium hydroxide, insulation finishes to be cooled to 10 ℃; A large amount of white solids, reaction finishes, and filters; Dry 4-(2-hydroxyethyl sulfone) the Acetanilide bullion that gets, fusing point: 192 ~ 197 ℃, purity is greater than 96% (HPLC).Bullion is joined recrystallization gets the elaboration white crystalline solid, 197.5 ~ 198.8 ℃ of fusing points, content 99.41% (HPLC) in 95% ethanol of 9 times of weight.
Embodiment 4
In reaction vessel, add entry 600mL, S-WAT 1.3mol, sodium hydrogencarbonate 5mol under agitation evenly drops into 4-ASC 1mol; Controlled temperature is below 30 ℃, and feeding intake finishes, and heats up, and makes temperature between 30 ~ 35 ℃, react 2h; Feed liquid becomes yellow by white, is cooled to 10 ℃, suction filtration, filtering inorganic salt; Filtrating uses 30% salt acid out to pH1, separates out white produce article, suction filtration, 60 ℃ of dry 4-kharophen benzene sulfinic acids that get.
In reaction vessel, add glycol chlorohydrin 1.5mol, add 4-kharophen benzene sulfinic acid 1mol, feed liquid is muddy; Be brown, transfer pH 7.5 with 20% sodium hydroxide, feed liquid is transparent; Slowly be warming up to 96 ~ 100 ℃, and under this temperature, be incubated 8h, constantly transfer pH that it is kept between 7.5 ~ 8 in the process with 20% sodium hydroxide; Insulation finishes to be cooled to 10 ℃ of a large amount of white solids, and reaction finishes, and filters; Dry 4-(2-hydroxyethyl sulfone) the Acetanilide bullion that gets, fusing point: 192 ~ 197 ℃, content is greater than 96% (HPLC).Above-mentioned bullion joins that recrystallization gets the elaboration white crystalline solid, 197.3 ~ 198.5 ℃ of fusing points, content 99.45% (HPLC) in 95% ethanol of 12 times of weight.
Claims (5)
1. a method for preparing 4-(2-hydroxyethyl sulfone) Acetanilide is characterized in that: 30 ~ 35 ℃ of temperature controls, reaction water, 4-ASC, S-WAT and sodium bicarbonate 1.5 ~ 2h; Cooling; Suction filtration filtering salinity, filtrating adds hcl acidifying, and suction filtration gets 4-kharophen benzene sulfinic acid; 4-kharophen benzene sulfinic acid is suspended in the water, transfers pH7.5 ~ 8, drip glycol chlorohydrin, 96 ~ 100 ℃ of temperature controls, control pH7.5 ~ 8 insulations, 8 ~ 10h, product is separated out in cooling.
2. the method for preparing 4-(2-hydroxyethyl sulfone) Acetanilide according to claim 1, it is characterized in that: the mol ratio of 4-ASC, S-WAT and sodium bicarbonate is 1:1 ~ 1.3:3 ~ 4.
3. the method for preparing 4-(2-hydroxyethyl sulfone) Acetanilide according to claim 1 is characterized in that: after reaction finishes, with 95% ethanol refined prod.
4. the method for preparing 4-(2-hydroxyethyl sulfone) Acetanilide according to claim 3, it is characterized in that: 95% consumption of ethanol is 9 ~ 12 times of product weight.
5. the method for preparing 4-(2-hydroxyethyl sulfone) Acetanilide according to claim 1 is characterized in that concrete steps comprise:
(1) water, S-WAT, sodium bicarbonate are added in the reaction flask, adjust the temperature to 35 ~ 40 ℃, slowly add the 4-ASC; 30 ℃ of temperature controls, the reinforced end, reaction 1.5 ~ 2h; Material is cooled to 10 ℃, the filtering salinity, filtrating adds the hydrochloric acid acid out to pH1; Filtration drying gets 4-kharophen benzene sulfinic acid; Wherein, the amount ratio of 4-ASC, S-WAT, sodium bicarbonate and water is 1mol:1 ~ 1.3mol:3 ~ 5mol:600mL;
(2) with in the 4-kharophen benzene sulfinic acid sodium adding glycol chlorohydrin, dropwise liquid is regulated pH7.5 ~ 8,96 ~ 100 ℃ of temperature controls, and control pH7.5 ~ 8 keep 8 ~ 10h, are cooled to 10 ℃, filter 60 ℃ of dry 4-(2-hydroxyethyl sulfone) Acetanilide bullions that get; Wherein, the mol ratio of glycol chlorohydrin and 4-kharophen benzene sulfinic acid is 1.2 ~ 1.5:1;
(3) get 4-(2-hydroxyethyl sulfone) Acetanilide (2) elaboration with the refining bullion of 95% ethanol, 95% amount of ethanol is 9 ~ 12 times of bullion weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103665003A CN102442929A (en) | 2011-11-18 | 2011-11-18 | Method for preparing 4- (2-hydroxyethyl sulfone) acetanilide |
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| CN2011103665003A CN102442929A (en) | 2011-11-18 | 2011-11-18 | Method for preparing 4- (2-hydroxyethyl sulfone) acetanilide |
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| CN102442929A true CN102442929A (en) | 2012-05-09 |
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| CN2011103665003A Pending CN102442929A (en) | 2011-11-18 | 2011-11-18 | Method for preparing 4- (2-hydroxyethyl sulfone) acetanilide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151213A (en) * | 2014-07-16 | 2014-11-19 | 常州大学 | Method for preparing arylformic acid from carbon dioxide |
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| US4612394A (en) * | 1982-04-06 | 1986-09-16 | Sumitomo Chemical Company, Limited | Process for producing aminophenyl-β-hydroxyethylsulfone |
| EP1170285A1 (en) * | 2000-07-06 | 2002-01-09 | Konica Corporation | A process for preparing a sulfinate |
| CN1800160A (en) * | 2005-10-08 | 2006-07-12 | 浙江大学 | 3-amido-4-alkylamino lauseto neu preparation method |
-
2011
- 2011-11-18 CN CN2011103665003A patent/CN102442929A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4612394A (en) * | 1982-04-06 | 1986-09-16 | Sumitomo Chemical Company, Limited | Process for producing aminophenyl-β-hydroxyethylsulfone |
| EP1170285A1 (en) * | 2000-07-06 | 2002-01-09 | Konica Corporation | A process for preparing a sulfinate |
| CN1800160A (en) * | 2005-10-08 | 2006-07-12 | 浙江大学 | 3-amido-4-alkylamino lauseto neu preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151213A (en) * | 2014-07-16 | 2014-11-19 | 常州大学 | Method for preparing arylformic acid from carbon dioxide |
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