CN100999478A - Process of preparing serine - Google Patents
Process of preparing serine Download PDFInfo
- Publication number
- CN100999478A CN100999478A CN 200610020148 CN200610020148A CN100999478A CN 100999478 A CN100999478 A CN 100999478A CN 200610020148 CN200610020148 CN 200610020148 CN 200610020148 A CN200610020148 A CN 200610020148A CN 100999478 A CN100999478 A CN 100999478A
- Authority
- CN
- China
- Prior art keywords
- serine
- chloracetyl
- acetyl
- sweet ammonia
- glycine
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention is a new preparation method of DL-serine. It takes acetoglycocol,acetoglycinate, chloracetylglycocol or chloracetoglycinate, and 37% formaldehyde solution as materials, in alkaline conditions and under certain temperature, through reaction for certain time, after acidification to isolate DL-serine.
Description
The present invention relates to the novel method of DL-serine preparation.Be the novel method that raw material prepares DL-serine particularly with acetyl glycine, acetyl glycine ester, chloracetyl glycine, chloracetyl glycinate, formaldehyde etc.
Serine is a kind of non-natural glycoprotein amino acid in half a lifetime.Not only can be used for food and feed additive, at present, be widely used in field of medicaments, have very wide application prospect.Its preparation method mainly comprises proteolysis extraction method, biological enzyme, precursor fermentation method, chemical synthesis.At present, domestic minority producer adopts the hydrolysis extraction method, this method complicated operation, seriously polluted and have high input, output is low, is unfavorable for big production.The other biological method drops into bigger then because of with high content of technology.
The object of the present invention is to provide that a kind of simple to operate, operational path is short, by product is few, the novel method of the DL--Serine preparation that yield is higher.
For reaching above-mentioned purpose, the present invention adopts following scheme: the novel method of DL-serine preparation comprises the following steps: that (1) is raw material with acetyl glycine or the sweet ammonia ester of acetyl: sweet ammonia ester of a part acetyl glycine or acetyl and 37% formaldehyde solution are at alkaline condition, certain temperature reaction certain hour, acidified separation obtains a part DL-serine (seeing formula one); (2) be raw material with chloracetyl glycine or the sweet ammonia ester of chloracetyl: sweet ammonia ester of chloracetyl glycine or chloracetyl and 37% formaldehyde solution are at alkaline condition, certain temperature reaction certain hour, acidified, hydrolysis, separation obtain two molecule DL-serine (seeing formula two).
The sweet ammonia ester of the used acetyl of the present invention mainly is meant sweet ammonia methyl esters of acetyl or the sweet ammonia ethyl ester of acetyl; The sweet ammonia ester of used chloracetyl mainly is meant sweet ammonia methyl esters of chloracetyl or the sweet ammonia ethyl ester of chloracetyl; Used formaldehyde solution concentration is the 5-40% aqueous solution; The used alkali of the present invention is that a kind of independent or several mixing in yellow soda ash, sodium bicarbonate, saleratus, salt of wormwood, sodium hydroxide or the potassium hydroxide are used; Temperature of reaction of the present invention is 5-120 ℃, and the best is 30-80 ℃; Reaction times of the present invention is 2-72 hour, and the best is 8-24 hour.The present invention simple to operate, raw materials used cheap and easy to get, by product is few, has greatly saved cost.
Further specify the present invention below by example:
Embodiment one:
In the 2000ml there-necked flask, add 103g acetyl glycine (1mol) and 600ml methyl alcohol, after the stirring and dissolving, add 168gNaHCO
3(2mol) and a spot of formol polymerization retarder, and slowly drip the formaldehyde solution (1.5mol) of 121.6g37-40%, temperature rises, after dropwising, warming-in-water to 50 ℃, isothermal reaction 8h is after reaction stops, after concentrating methyl alcohol and water, with the residue dissolve with methanol, filter out inorganic salt again.Be concentrated into gained filtrate dried, gains 500m14NHCl hydrolysis, transfer PH to 5-6 with strong aqua then, cold filtration, the gained solid is the DL-serine crude product, and the gained crude product dissolves with 500ml boiling water, then with 1000ml dehydrated alcohol precipitation, after filtration, washing, drying, can get DL-serine 76g, yield is 72%.
Embodiment two:
In the 2000ml there-necked flask, add 117g acetyl glycine methyl esters (1mol) and 600ml methyl alcohol, after the stirring and dissolving, add 138gK
2CO
3(1mol) and a spot of formol polymerization retarder, and slowly drip the formaldehyde solution (1.5mol) of 121.6g37-40%, temperature rises, after dropwising, and warming-in-water to 40 ℃, isothermal reaction 12h.All the other subsequent disposal are referring to embodiment one, and last products obtained therefrom is 71.5g, and yield is 69%.
Embodiment three:
In the 2000ml there-necked flask, add 131g acetyl glycine ethyl ester (1mol) and 800ml methyl alcohol, after the stirring and dissolving, add 106gNa
2CO
3(1mol) and a spot of formol polymerization retarder, and slowly drip the formaldehyde solution (1.5mol) of 121.6g37-40%, temperature rises, after dropwising, and warming-in-water to 55 ℃, isothermal reaction 16h.All the other subsequent disposal are referring to embodiment one. and last products obtained therefrom is 57g, and yield is 54%.
Embodiment four:
In the 2000ml there-necked flask, add 131g acetyl glycine ethyl ester (1mol) and 800ml methyl alcohol, after the stirring and dissolving, add 40gNaOH (1mol) and a spot of formol polymerization retarder, and slowly drip the formaldehyde solution (1.5mol) of 121.6g37-40%, temperature rises, after dropwising, warming-in-water to 45 ℃, isothermal reaction 16h.All the other subsequent disposal are referring to embodiment one, and last products obtained therefrom is 63g, and yield is 60%.
Embodiment five:
In the 500ml there-necked flask, add 16.6gN-chloracetyl glycine methyl ester (0.1mol) and 120ml methyl alcohol, after the stirring and dissolving, add 40gKHCO
3(0.4mol) and a small amount of formol polymerization retarder, slowly drip the formaldehyde solution of 32.4g37-40%, 50 ℃ of heating in water bath, back flow reaction 24h.After concentrating methyl alcohol and water, with the residue dissolve with methanol, filter out inorganic salt again.The gained colourless liquid is crossed silicagel column, use earlier ethyl acetate: sherwood oil=5: 1 dashes with methyl alcohol at last towards post.Collect the methyl alcohol washing lotion, when being concentrated to no methyl alcohol, can getting colourless liquid and be N-(2-methylol) chloracetyl-DL-serine methyl esters, yield is 78%.
After in the 2000ml there-necked flask, adding 225.5 gram N-(2-methylol) chloracetyl-DL-serine methyl esters and 500ml dissolve with methanol, add the solution that 80g sodium hydroxide and 800ml water are made into, reflux 2-3 hour.Behind the stopped reaction, the PH that transfers reaction solution with 4NHCL is to 5-6, and cold filtration adds the gained solid in the hydrogenation still, adds 300 gram liquefied ammonia and 20 gram bicarbonate of ammonia then, heats 12 hours under 90-100 ℃.After the reactor cooling, bleed off ammonia, derive reaction solution, transfer PH to 5-6 with 4NHCl, cooling, filtration, washing gained solid are the DL-serine crude product, and crude product dissolves through boiling water, can get product 151 grams behind the dehydrated alcohol recrystallization, and yield is 72%.
Embodiment six:
In the 500ml there-necked flask, add 18gN-chloracetyl glycine ethyl ester (0.1mol) and 150ml methyl alcohol, after the stirring and dissolving, add 16.6g (0.12mol) salt of wormwood and a small amount of formol polymerization retarder, slowly drip the formaldehyde solution of 32.4g37-40%, temperature is on the rise.After the temperature-stable, be warmed up to 40 ℃, heating in water bath refluxes, reaction 20h.Can obtain N-(2-methylol) chloracetyl-DL-serine ethyl ester, subsequent disposal can obtain DL-serine 16.9g at last referring to embodiment five, and yield is 80%.
Embodiment seven:
In the 500ml there-necked flask, add 18gN-chloracetyl glycine ethyl ester (0.1mol) and 150ml methyl alcohol, after the stirring and dissolving, add 40gKHCO
3(0.4mol) and a small amount of formol polymerization retarder, slowly drip the formaldehyde solution of 32.4g37-40%, temperature is on the rise.After the temperature-stable, be warmed up to 45 ℃, heating in water bath refluxes, reaction 48h.Can obtain N-(2-methylol) chloracetyl-DL-serine ethyl ester, subsequent disposal can obtain DL-serine 14.7g at last referring to embodiment five, and yield is 70%.
Embodiment eight:
In the 500ml there-necked flask, add 18gN-chloracetyl glycine ethyl ester (0.1mol) and 150ml methyl alcohol, after the stirring and dissolving, add 24gNaOH (0.6mol) and a small amount of formol polymerization retarder. slowly drip the formaldehyde solution of 32.4g37-40%, temperature is on the rise.After the temperature-stable, be warmed up to 45 ℃, heating in water bath refluxes, reaction 24h.Can obtain N-(2-methylol) chloracetyl-DL-serine ethyl ester, subsequent disposal can obtain DL-serine 10.1g at last referring to embodiment five, and yield is 48%.
Claims (5)
- The novel method of 1 one kinds of DL-serine preparations.Be to be the novel method that raw material prepares DL-serine with acetyl glycine, acetyl glycine ester, chloracetyl glycine, chloracetyl glycinate, formaldehyde etc.(1) be raw material with acetyl glycine or the sweet ammonia ester of acetyl: sweet ammonia ester of a part acetyl glycine or acetyl and 37% formaldehyde solution is at alkaline condition, certain temperature reaction certain hour, and acidified separation obtains a part DL-serine; (2) be raw material with chloracetyl glycine or the sweet ammonia ester of chloracetyl: sweet ammonia ester of chloracetyl glycine or chloracetyl and 37% formaldehyde solution is at alkaline condition, certain temperature reaction certain hour, and acidified, hydrolysis, separation obtain two molecule DL-serine.
- 2 DL-serine novel preparation methods according to claim 1 is characterized in that, the sweet ammonia ester of used acetyl mainly is meant sweet ammonia methyl esters of acetyl or the sweet ammonia ethyl ester of acetyl; The sweet ammonia ester of used chloracetyl mainly is meant sweet ammonia methyl esters of chloracetyl or the sweet ammonia ethyl ester of chloracetyl.
- 3 DL-serine novel preparation methods according to claim 1 is characterized in that used formaldehyde solution concentration is the 5-40% aqueous solution.
- 4 DL-serine novel preparation methods according to claim 1 is characterized in that, used alkali is that a kind of independent or several mixing in yellow soda ash, sodium bicarbonate, saleratus, salt of wormwood, sodium hydroxide or the potassium hydroxide are used.
- 5 DL-serine novel preparation methods according to claim 1 is characterized in that temperature of reaction is 5-120 ℃, and the best is 30-80 ℃; Reaction times of the present invention is 2-72 hour, and the best is 8-24 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610020148 CN100999478A (en) | 2006-01-13 | 2006-01-13 | Process of preparing serine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610020148 CN100999478A (en) | 2006-01-13 | 2006-01-13 | Process of preparing serine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN100999478A true CN100999478A (en) | 2007-07-18 |
Family
ID=38258315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610020148 Pending CN100999478A (en) | 2006-01-13 | 2006-01-13 | Process of preparing serine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100999478A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168513B (en) * | 2007-11-28 | 2012-06-27 | 上海化学试剂研究所 | Method for preparing DL-serine |
| CN107365260A (en) * | 2017-07-31 | 2017-11-21 | 长沙道勤生物科技有限公司 | The preparation method of feed addictive serine |
| CN110373440A (en) * | 2019-07-23 | 2019-10-25 | 长兴制药股份有限公司 | The method of one pot of enzyme process preparation DL-serine |
-
2006
- 2006-01-13 CN CN 200610020148 patent/CN100999478A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168513B (en) * | 2007-11-28 | 2012-06-27 | 上海化学试剂研究所 | Method for preparing DL-serine |
| CN107365260A (en) * | 2017-07-31 | 2017-11-21 | 长沙道勤生物科技有限公司 | The preparation method of feed addictive serine |
| CN110373440A (en) * | 2019-07-23 | 2019-10-25 | 长兴制药股份有限公司 | The method of one pot of enzyme process preparation DL-serine |
| CN110373440B (en) * | 2019-07-23 | 2022-03-01 | 长兴制药股份有限公司 | Method for preparing DL-serine by one-pot enzyme method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100999516A (en) | Purifying process of glycolide | |
| CN102558572B (en) | Method for preparing xylogen acetylated derivative in ionic liquid solvent | |
| CN101735123A (en) | Method for synthesizing valnemulin hydrochloride | |
| CN103508878B (en) | A kind of method of being prepared high purity ethanol acid crystal by methyl glycollate | |
| CN101760483A (en) | Method for preparing high-purity resveratrol from fresh giant knotweed rhizome | |
| CN100999478A (en) | Process of preparing serine | |
| CN103387593B (en) | A kind of method of coproduction maltonic acid-delta-lactone, seminose and N.F,USP MANNITOL | |
| CN101701234B (en) | Method for extracting ellagic acid in pomegranate peel residue by using biological enzyme | |
| CN102617374B (en) | Method for preparing betaine hydrochloride | |
| CN102260596B (en) | Method for preparing biodiesel by two-step process | |
| CN103288630A (en) | Synthesizing method of Salvianic acid A sodium | |
| CN103804173A (en) | Fermentation organic acid refining method | |
| CN103214421B (en) | The industrialized preparing process of 2-sulfydryl-1-Methylimidazole | |
| CN102093173A (en) | Method for preparing 3-ethyoxyl-1,2-propylene glycol by directly esterifying glycerol and ethanol | |
| CN101050206A (en) | Method for preparing Repaglinide | |
| CN103304467A (en) | Method for preparing N-coffee acyl tryptamine by one-step process | |
| CN103467350B (en) | (S) preparation method of-AzeOH | |
| CN107739296B (en) | Method for collecting oleic acid from tea oil | |
| CN104725437A (en) | Method for preparation of laminaribiose and rebaudiodside B by basic hydrolysis of rebaudiodside I | |
| CN101624612B (en) | Method for catalytic synthesis of glycoside esters compound by immobilized penicillium expansum lipase | |
| CN103467324B (en) | Preparation method of N, N-dimethylglycine for industrial production | |
| CN103664654A (en) | Industrial production method of high-purity sulfuric acid terbutaline | |
| CN102453736A (en) | Method for preparing quercetin by enzyme reaction of hyperoside | |
| CN106432386A (en) | Method for synthesizing neohesperidin by taking naringin as raw material | |
| CN103553909B (en) | The method of o-ethoxybenzoic acid is synthesized with Whitfield's ointment and acetone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20070718 |