CN102399174A - Synthesis method of 2-aminoethanesulfinic acid - Google Patents
Synthesis method of 2-aminoethanesulfinic acid Download PDFInfo
- Publication number
- CN102399174A CN102399174A CN2011103940655A CN201110394065A CN102399174A CN 102399174 A CN102399174 A CN 102399174A CN 2011103940655 A CN2011103940655 A CN 2011103940655A CN 201110394065 A CN201110394065 A CN 201110394065A CN 102399174 A CN102399174 A CN 102399174A
- Authority
- CN
- China
- Prior art keywords
- ethylamine
- sulfinic acid
- compound method
- acid according
- sulfoxylate
- 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.)
- Pending
Links
- VVIUBCNYACGLLV-UHFFFAOYSA-N hypotaurine Chemical compound [NH3+]CCS([O-])=O VVIUBCNYACGLLV-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 17
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- ARSOBUPZTZPUSZ-UHFFFAOYSA-N S(O)O.N Chemical compound S(O)O.N ARSOBUPZTZPUSZ-UHFFFAOYSA-N 0.000 claims description 3
- ZTTJIWQWPIRCSK-UHFFFAOYSA-N [K].S(O)O Chemical compound [K].S(O)O ZTTJIWQWPIRCSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- WSYUEVRAMDSJKL-UHFFFAOYSA-N ethanolamine-o-sulfate Chemical compound NCCOS(O)(=O)=O WSYUEVRAMDSJKL-UHFFFAOYSA-N 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 235000012970 cakes Nutrition 0.000 description 13
- 238000002386 leaching Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 235000021463 dry cake Nutrition 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229960003080 taurine Drugs 0.000 description 2
- 208000006558 Dental Calculus Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of 2-aminoethanesulfinic acid, which comprises the step of carrying out nucleophilic substitution reaction on ethanolamine sulfate and sulfites under the protection of gas to obtain the 2-aminoethanesulfinic acid. Through the way, the method can obtain the 2-aminoethanesulfinic acid with ideal yield under the condition of simple process conditions.
Description
Technical field
The present invention relates to the synthetic field of organic chemistry, particularly relate to a kind of compound method of 2-ethylamine-sulfinic acid.
Background technology
2-ethylamine-sulfinic acid, have another name called hypotaurine (see " general biochemistry "/Zheng Ji, Chen Junhui writes. the third edition, Beijing, Higher Education Publishing House, 1998.7, P440), molecular formula is NH
2CH
2CH
2SO
2H, molecular weight is 109.2, be white in color crystallization or powder are soluble in water.
2-ethylamine-sulfinic acid is a kind of important midbody of sulfur-bearing amino acid cysteine synthesized taurine in the organism, so it can substitute halfcystine and comes synthesized taurine in vivo.At present, its disclosed chemical synthesis process is not arranged as yet.
Summary of the invention
The technical problem that the present invention mainly solves provides and can under the simple condition of processing condition, obtain the compound method of a kind of 2-ethylamine-sulfinic acid of ideal yield.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is: the compound method that a kind of 2-ethylamine-sulfinic acid is provided; Its compound method is that thanomin sulfuric ester and sulfoxylate are carried out nucleophilic substitution reaction under the protection of gas, obtains 2-ethylamine-sulfinic acid.
Preferably, the mass percent of described sulfoxylate is >=85%.
More excellent is that the mass percent of described thanomin sulfuric ester is >=98%.
More excellent is that the mol ratio of described thanomin sulfuric ester and sulfoxylate is 1:1-2.
More excellent is that the mol ratio of described thanomin sulfuric ester and sulfoxylate is 1:1.3-1.5.
More excellent is that said sulfoxylate is any one of sodium hydrosulfite 90min, sulfoxylic acid potassium or sulfoxylic acid ammonium.
More excellent is that described nucleophilic substitution reaction is that temperature of reaction is controlled to be 80-150 ℃, will the time be controlled to be 6-36h.
More excellent is that described nucleophilic substitution reaction is that temperature of reaction is controlled to be 100-120 ℃, will the time be controlled to be 20-24h.
More excellent is, described gas is nitrogen, any one or its combination of hydrogen or dioxide gas.
The invention has the beneficial effects as follows: the technology of the compound method of 2-ethylamine-sulfinic acid of the present invention is terse, and reaction yield is high, thereby satisfies the industrial amplification production requirement.
Embodiment
Set forth in detail in the face of preferred embodiment of the present invention down, thereby protection scope of the present invention is made more explicit defining so that advantage of the present invention and characteristic can be easier to it will be appreciated by those skilled in the art that.
The reaction formula of the compound method of 2-ethylamine-sulfinic acid of the present invention is:
NH
2CH
2CH
2OSO
3H+Na
2SO
2 
NH
2CH
2CH
2SO
2H+Na
2SO
4
Embodiment 1:
Stir at 1000 milliliters of bands, in the stainless steel autoclave of heating and cooling device, be full of nitrogen earlier, under agitation thanomin sulfuric ester 287.7g (98%) and sodium hydrosulfite 90min 258.8g (85%) are added in the entry; Be warming up to 80 ℃ then, controlled temperature is at 80 ℃, and pressure is normal pressure, insulation reaction 36 hours; Stop heating, remove by filter sodium sulfate at 80 ℃, and with 200 ml water washing leaching cakes; Merging filtrate is cooled to 5 ℃, filters; And with 200 ml water washing leaching cakes, dry cake gets 2-ethylamine-sulfinic acid finished product 69.2g.Yield is 31.74%.
Embodiment 2:
Stir at 1000 milliliters of bands, in the stainless steel autoclave of heating and cooling device, be full of hydrogen earlier, under agitation thanomin sulfuric ester 287.7g (98%) and sulfoxylic acid potassium 501g (85%) are added in the entry; Be warming up to 110 ℃ then, controlled temperature is at 110 ℃, and pressure is normal pressure, insulation reaction 22 hours; Stop heating, be cooled to 80 ℃, remove by filter vitriolate of tartar at 80 ℃, and with 200 ml water washing leaching cakes; Merging filtrate is cooled to 5 ℃, filters; And with 200 ml water washing leaching cakes, dry cake gets 2-ethylamine-sulfinic acid finished product 129.4g.Yield is 59.36%.
Embodiment 3:
Stir at 1000 milliliters of bands, in the stainless steel autoclave of heating and cooling device, be full of nitrogen earlier, under agitation thanomin sulfuric ester 287.7 (98%) g and sodium hydrosulfite 90min 517.6g (85%) are added in the entry; Be warming up to 80 ℃ then, controlled temperature is at 150 ℃, and pressure is 0.3MPa, insulation reaction 6 hours; Stop heating, pressure is reduced to normal pressure, and temperature is reduced to 80 ℃, removes by filter sodium sulfate at 80 ℃; And with 200 ml water washing leaching cakes, merging filtrate is cooled to 5 ℃, filters; And with 200 ml water washing leaching cakes, dry cake gets 2-ethylamine-sulfinic acid finished product 79.1g.Yield is 36.26%.
Embodiment 4:
Stir at 1000 milliliters of bands, in the stainless steel autoclave of heating and cooling device, be full of nitrogen earlier, under agitation thanomin sulfuric ester 287.7 (98%) g and sulfoxylic acid ammonium 329.4g (85%) are added in the entry; Be warming up to 120 ℃ then, controlled temperature is at 120 ℃, and pressure is 0.1MPa, insulation reaction 20 hours; Stop heating, pressure is reduced to normal pressure, and temperature is reduced to 5 ℃ of filtrations, gets filter cake also with 200 ml water heating for dissolving; Be cooled to 5 ℃, filter, and with 100 ml water washing leaching cakes; Dry cake, dry cake gets 2-ethylamine-sulfinic acid finished product 131.2g.Yield is 60.18%.
Embodiment 5:
Stir at 1000 milliliters of bands, in the stainless steel autoclave of heating and cooling device, be full of nitrogen earlier, under agitation thanomin sulfuric ester 287.7 (98%) g and sodium hydrosulfite 90min 414.1g (85%) are added in the entry; Be warming up to 100 ℃ then, controlled temperature is at 100 ℃, and pressure is normal pressure, insulation reaction 24 hours; Stop heating, temperature is reduced to 80 ℃, removes by filter sodium sulfate at 80 ℃, and with 200 ml water washing leaching cakes; Merging filtrate is cooled to 5 ℃, filters; And with 200 ml water washing leaching cakes, dry cake gets 2-ethylamine-sulfinic acid finished product 99.2g.Yield is 45.5%.
Embodiment 6:
Stir at 1000 milliliters of bands, in the stainless steel autoclave of heating and cooling device, be full of nitrogen earlier, under agitation thanomin sulfuric ester 287.7 (98%) g and sodium hydrosulfite 90min 366.6g (90%) are added in the entry; Be warming up to 110 ℃ then, controlled temperature is at 110 ℃, and pressure is normal pressure, insulation reaction 23 hours; Stop heating, temperature is reduced to 80 ℃, removes by filter sodium sulfate at 80 ℃, and with 200 ml water washing leaching cakes; Merging filtrate is cooled to 5 ℃, filters; And with 200 ml water washing leaching cakes, dry cake gets 2-ethylamine-sulfinic acid finished product 145.2g.Yield is 66.61%.
Embodiment 7:
Stir at 1000 milliliters of bands, in the stainless steel autoclave of heating and cooling device, be full of dioxide gas earlier, under agitation thanomin sulfuric ester 286.2 (98.5%) g and sodium hydrosulfite 90min 366.6g (90%) are added in the entry; Be warming up to 80 ℃ then, controlled temperature is at 115 ℃, and pressure is normal pressure, insulation reaction 28 hours; Stop heating, temperature is reduced to 80 ℃, removes by filter sodium sulfate at 80 ℃, and with 200 ml water washing leaching cakes; Merging filtrate is cooled to 5 ℃, filters; And with 200 ml water washing leaching cakes, dry cake gets 2-ethylamine-sulfinic acid finished product 133.2g.Yield is 61.01%.
The synthetic method craft of 2-ethylamine-sulfinic acid of the present invention is terse, and reaction yield is high, thereby satisfies the industrial amplification production requirement.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (9)
1. the compound method of a 2-ethylamine-sulfinic acid, it is characterized in that: its compound method is that thanomin sulfuric ester and sulfoxylate are carried out nucleophilic substitution reaction under the protection of gas, obtains 2-ethylamine-sulfinic acid.
2. the compound method of a kind of 2-ethylamine-sulfinic acid according to claim 1 is characterized in that: the mass percent of described sulfoxylate is >=85%.
3. the compound method of a kind of 2-ethylamine-sulfinic acid according to claim 1 is characterized in that: the mass percent of described thanomin sulfuric ester is >=98%.
4. the compound method of a kind of 2-ethylamine-sulfinic acid according to claim 1 is characterized in that: the mol ratio of described thanomin sulfuric ester and sulfoxylate is 1:1-2.
5. the compound method of a kind of 2-ethylamine-sulfinic acid according to claim 4 is characterized in that: the mol ratio of described thanomin sulfuric ester and sulfoxylate is 1:1.3-1.5.
6. the compound method of a kind of 2-ethylamine-sulfinic acid according to claim 1 is characterized in that: said sulfoxylate is any one of sodium hydrosulfite 90min, sulfoxylic acid potassium or sulfoxylic acid ammonium.
7. the compound method of a kind of 2-ethylamine-sulfinic acid according to claim 1 is characterized in that: described nucleophilic substitution reaction is that temperature of reaction is controlled to be 80-150 ℃, will the time be controlled to be 6-36h.
8. the compound method of a kind of 2-ethylamine-sulfinic acid according to claim 7 is characterized in that: described nucleophilic substitution reaction is that temperature of reaction is controlled to be 100-120 ℃, will the time be controlled to be 20-24h.
9. the compound method of a kind of 2-ethylamine-sulfinic acid according to claim 1 is characterized in that: described gas is nitrogen, any one of hydrogen or dioxide gas or its combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103940655A CN102399174A (en) | 2011-12-02 | 2011-12-02 | Synthesis method of 2-aminoethanesulfinic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103940655A CN102399174A (en) | 2011-12-02 | 2011-12-02 | Synthesis method of 2-aminoethanesulfinic acid |
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| Publication Number | Publication Date |
|---|---|
| CN102399174A true CN102399174A (en) | 2012-04-04 |
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|---|---|---|---|
| CN2011103940655A Pending CN102399174A (en) | 2011-12-02 | 2011-12-02 | Synthesis method of 2-aminoethanesulfinic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108341758A (en) * | 2018-03-09 | 2018-07-31 | 宁波百思佳医药科技有限公司 | A kind of synthetic method of 2- aminoethanes sulfinic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0823421A1 (en) * | 1995-04-21 | 1998-02-11 | Sogo Pharmaceutical Company Limited | Process for producing taurine analogues |
| CN1203910A (en) * | 1998-06-02 | 1999-01-06 | 中国科学院上海有机化学研究所 | Method for preparing 2,2,2-trifluoro-ethylsulfinate and its derivant |
| CN1237156A (en) * | 1997-10-02 | 1999-12-01 | L·布鲁克曼两合公司 | Sulphinic acid derivatives, method for producing them, and their use |
-
2011
- 2011-12-02 CN CN2011103940655A patent/CN102399174A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0823421A1 (en) * | 1995-04-21 | 1998-02-11 | Sogo Pharmaceutical Company Limited | Process for producing taurine analogues |
| CN1237156A (en) * | 1997-10-02 | 1999-12-01 | L·布鲁克曼两合公司 | Sulphinic acid derivatives, method for producing them, and their use |
| CN1203910A (en) * | 1998-06-02 | 1999-01-06 | 中国科学院上海有机化学研究所 | Method for preparing 2,2,2-trifluoro-ethylsulfinate and its derivant |
Non-Patent Citations (1)
| Title |
|---|
| 杨洁等，: "牛磺酸合成工艺的优化", 《化工进展》, vol. 24, no. 11, 31 December 2005 (2005-12-31), pages 1269 - 1270 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108341758A (en) * | 2018-03-09 | 2018-07-31 | 宁波百思佳医药科技有限公司 | A kind of synthetic method of 2- aminoethanes sulfinic acid |
| CN108341758B (en) * | 2018-03-09 | 2020-11-27 | 宁波百思佳医药科技有限公司 | Synthesis method of 2-aminoethanesulfinic acid |
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Application publication date: 20120404 |