CN100417645C - Method of synthesizing selenium methyl selenium substituted cysteine through methyl seleno acetaldehyde - Google Patents
Method of synthesizing selenium methyl selenium substituted cysteine through methyl seleno acetaldehyde Download PDFInfo
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- CN100417645C CN100417645C CNB2006101249426A CN200610124942A CN100417645C CN 100417645 C CN100417645 C CN 100417645C CN B2006101249426 A CNB2006101249426 A CN B2006101249426A CN 200610124942 A CN200610124942 A CN 200610124942A CN 100417645 C CN100417645 C CN 100417645C
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- methylselenocysteinefrom
- acetaldehyde
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Abstract
The present invention discloses a method capable of utilizing methylselenoacetaldehyde to synthesize selenomethyl selenocysteine. It is characterized by that said method includes the following steps; firstly, utilizing existent technological process to prepare dimethyl diselenide and methyl-hydroselenide salt; then making methyl-hydroselenide salt and halogenated acetaldehyde produce reaction to obtain methylselenoacetaldehyde; and utilizing the methylselenoacetaldehyde to prepare methylsoleno methylintraureide, then using said methylseleno methylintraureide to prepare the invented selenomethyl selenocysteine.
Description
Technical field
The present invention relates to amino acid medicine synthetic method, especially relate to a kind of method by the synthetic methylselenocysteinefrom of first seleno acetaldehyde.
Background technology
Selenium is the necessary trace element of human body, and it is the moiety of red corpuscle Selenoperoxidase, and it mainly acts on is participate in enzyme synthetic, and the structure and the function of protection cytolemma exempt from over oxidation and interference.Selenium deficiency will cause that closing the selenium enzymic activity reduces, and oxygen radical removing is obstructed, the microbial film damage, and detoxifcation and immunologic function a series of body function obstacles such as go down, thus cause multiple disease generation.That selenium has is anticancer, give protection against cancer, protect heart, prevent and treat cataract, prevent and treat Keshan disease and Kaschin-Beck disease, delay senility, separate functions such as heavy metal poison.Have more than 40 countries and regions to lack selenium at present in the world, China has people more than 100,000,000 to lack selenium or low selenium, suffers from or very easily generation and scarce selenium diseases associated.For the shortage of selenium, domestic inorganic salt Sodium Selenite sheet or the Sodium Selenite nutrient fortified food of generally utilizing replenishes, but inorganic selenium toxicity is bigger, forbidden for many countries or limits use; Then mainly utilize organic selenium compounds to replenish abroad, as selenium-enriched protein etc.Methylselenocysteinefrom is one of existence form of organoselenium in the rich selenium whole food (as selenium-enriched garlic), is a kind of stable, efficient, safe benefit selenium composition.It is anticancer, anti-oxidant, anti-ageing that methylselenocysteinefrom has, and the treatment cardiovascular and cerebrovascular diseases is separated effects such as heavy metal poison, has been widely used in aspects such as medicine, nutritive health-care and agricultural.The production of natural selenium-rich food usually is subjected to the restriction of natural condition, and product selenium content instability; Utilize the synthetic methylselenocysteinefrom of chemical process then not to be subjected to the restriction of natural condition, product composition is single, and is stable and controllable for quality, is to produce the effective way of mending the selenium product.
At present methylselenocysteinefrom synthetic mainly contains following several method:
(1) chlorine L-Ala two sodium selenide methods: at first chlorine L-Ala and the reaction of two sodium selenides are generated selenocystine, use sodium Metal 99.5/liquefied ammonia (70 ℃) reductive cleavage then, get methylselenocysteinefrom with the methyl iodide alkylation again.This method relates to very low temperature and active hazardous metals sodium, severe reaction conditions, and processing unit requires high, chlorine L-Ala raw material sources difficulty, the cost height is difficult to scale operation (Tanaka, H; Soda, K; Selenocysteine.Methods Enzymol., 1987,143,240-243; Andreadou, I; Menge, W.M.P.B.; Commandeur, J.N.M.; Worthington, E.A.; Vermeulen, N.P.E.; J.Med.Chem., 1996,39,2040-2046);
(2) uncle's fourth oxygen acyl group protection Serine method: in the presence of basic phosphorus of three alkane (virtue) or phosphite; uncle's fourth oxygen acyl group Serine and the reaction of azoformic acid diester generate the β lactone; generate the methylselenocysteinefrom of uncle's fourth oxygen acyl group protection then with methyl-hydroselenide or its reactant salt, last deprotection gets methylselenocysteinefrom.This method technology is tediously long, and product yield is low, raw material thread propylhomoserin and protection reagent costliness, so production cost is very high, is difficult to scale operation (Spallholz, J.E.; Reid, T.W.; Walkup, R.D.; Amethod of using syntheticL-Se-methylselenocysteine as a nutraceuticaland a method of its synthesis, EP 1205471,2001);
(3) sodium methyl-hydroselenide replaces chlorine L-Ala method: the chlorine with in sodium methyl-hydroselenide replacement chlorine L-Ala or the chlorine alanine methyl ester gets methylselenocysteinefrom.This method is because of chlorine L-Ala raw material sources difficulty, and production cost is very high, is unfavorable for scale operation (Majeed; Muhammed (Piscataway, NJ); Nagabhushanam; Kalyanam (North Brunswick, NJ); Manufacturing processes forSe-methyl-L-selenocysteine, US 6794537B1,2004).
In sum, at present the methylselenocysteinefrom synthetic method has exists the raw material sources difficulty, costing an arm and a leg causes production cost too high, have have the operational path complexity, productive rate is low, product purity is low, what have exists defectives such as severe reaction conditions, equipment requirements height and difficult management, be unfavorable for scale operation, be difficult to satisfy the growing market requirement.
Summary of the invention
The object of the present invention is to provide that a kind of synthetic route is simple, raw material is easy to get cheaply, productive rate is high, easy to operate, cost is low, the methylselenocysteinefrom synthetic method of suitable large-scale industrial production.
Purpose of the present invention realizes by following synthetic method step:
(1) under 40-90 ℃ of temperature, reacts generation first seleno acetaldehyde with methyl-hydroselenide salt and halo acetaldehyde;
(2) first seleno acetaldehyde gets first seleno methylhydantoi with hydrochloric acid reaction then through reacting under 70-100 ℃ of temperature with volatile salt, sodium cyanide;
(3) first seleno methylhydantoi gets methylselenocysteinefrom salt through sodium hydroxide hydrolysis under 80-160 ℃ of temperature;
(4) methylselenocysteinefrom salt with acid (example hydrochloric acid etc.) acidifying neutralize methylselenocysteinefrom.
Concrete implementation step is:
(1) dimethyl diselenide ether (CH
3SeSeCH
3) preparation: in aqueous sodium hydroxide solution, the reaction of selenium powder and hydrazine hydrate generates sodium selenide, again with sodium selenide and methyl iodide or methyl-sulfate reaction, generation dimethyl diselenide ether, reaction equation is:
4Se+NH
2NH
2·H
2O+4NaOH→2Na
2Se
2+5H
2O+N
2
Na
2Se
2+2CH
3X→CH
3SeSeCH
3+2NaX
X=I or OSO
2OCH
3
(2) methyl-hydroselenide salt (CH
3SeM) preparation: DMF (N, dinethylformamide) solution, alkaline aqueous solution (sodium hydroxide, potassium hydroxide or ammoniacal liquor etc.) and sodium borohydride reaction with dimethyl diselenide ether, generate methyl-hydroselenide salt, reaction equation is:
4CH
3SeSeCH
3+NaBH
4+8MOH→8CH
3SeM+NaBO
2+6H
2O；
M=Na, K, NH
4, positively charged ion such as Li, Rb, Cs;
(3) first seleno acetaldehyde (CH
3SeCH
2CHO) preparation: methyl-hydroselenide salt (as sodium methyl-hydroselenide or methyl-hydroselenide potassium etc.) and halo acetaldehyde (as monochloroacetaldehyde or bromoacetaldehyde etc.) are reacted under 40-90 ℃ of temperature, generate first seleno acetaldehyde, reaction equation is as follows:
CH
3SeM+XCH
2CHO→CH
3SeCH
2CHO+MX
M=Na, K, NH
4, positively charged ion such as Li, Rb, Cs, halogens such as X=Cl, Br, I, F;
(4) preparation of first seleno methylhydantoi: first seleno acetaldehyde, volatile salt and sodium cyanide is water-soluble, after reacting by heating finishes under the 70-100 ℃ of temperature, be chilled to room temperature, add concentrated hydrochloric acid again, reacting by heating gets first seleno methylhydantoi;
(5) preparation of methylselenocysteinefrom salt: add first seleno methylhydantoi in sodium hydroxide solution, the reflux hydrolysis gets methylselenocysteinefrom sodium under 80-160 ℃ of temperature;
(6) preparation of methylselenocysteinefrom: methylselenocysteinefrom sodium is got methylselenocysteinefrom with hcl acidifying.
Described methyl-hydroselenide salt is a kind of in sodium methyl-hydroselenide, methyl-hydroselenide potassium, methyl-hydroselenide ammonium, methyl-hydroselenide lithium, methyl-hydroselenide rubidium or the methyl-hydroselenide caesium, and halo acetaldehyde is a kind of in monochloroacetaldehyde, bromoacetaldehyde, Jod-acetaldehyd or the fluorine acetaldehyde.
The glycolylurea method is that one of amino acid whose main method is produced in present industrial chemosynthesis, and this method cost is low, productive rate is high, mostly adopts this method to produce amino acid both at home and abroad.Aldehyde is that the glycolylurea method is produced amino acid whose important intermediate, by synthetic important intermediate first seleno acetaldehyde, can realize glycolylurea method production methylselenocysteinefrom.The present invention generates first seleno acetaldehyde by methyl-hydroselenide salt (as sodium salt or sylvite etc.) and halo acetaldehyde (as monochloroacetaldehyde or bromoacetaldehyde etc.) reaction, utilize first seleno acetaldehyde to prepare first seleno methylhydantoi then, make methylselenocysteinefrom by first seleno methylhydantoi more at last.This method has that synthetic route is simple, easy to operate, raw material is easy to get cheaply, high, the low cost and other advantages of productive rate, is fit to large-scale industrial production.
Description of drawings
Fig. 1 is a synthetic route synoptic diagram of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but should understands the non-scope that only limits to these embodiment of scope of the present invention.
Embodiment 1:
(1) dimethyl diselenide ether (CH
3SeSeCH
3) preparation (promptly prepared dimethyl diselenide ether) routinely: in the there-necked flask that dropping funnel and stirring are housed, add 500ml water, 80g sodium hydroxide stirs and adds the 158g selenium powder down; Cooling bath is chilled to below the room temperature, slowly drip 125g, 80% hydrazine hydrate again, about 30min added, in 25～32 ℃ of stirring reactions 2 hours, in about 20 ℃, stir then and drip the 284g methyl iodide down, added in about 1 hour, in 25～30 ℃ of stirring reactions 2 hours, standing demix, tell lower floor, through washing, get orange oily dimethyl diselenide 141 grams, yield 75%;
(2) sodium methyl-hydroselenide (CH
3SeNa) preparation (promptly prepared sodium methyl-hydroselenide) routinely: 50 gram dimethyl diselenide ethers are dissolved among 20 milliliters of DMF, stir and add 100 milliliters of 20% sodium hydroxide solutions down, solution is cooled to 5-10 ℃, and keep temperature to be lower than 10 ℃, slowly add sodium borohydride 6 grams in batches, after adding solution is incubated 2 hours in 40-45 ℃.The pressure reducing and steaming solvent is separated out white solid sodium methyl-hydroselenide 52 grams, yield 84%.
(3) first seleno acetaldehyde (CH
3SeCH
2CHO) preparation: add 100g monochloroacetaldehyde (40% aqueous solution) and 50g sodium methyl-hydroselenide in there-necked flask, 55 ℃ of following stirring and refluxing 3 hours must first seleno acetaldehyde 50g, yield 85%.
(4) preparation of first seleno methylhydantoi: get 40 gram volatile salts, 12 gram sodium cyanides in reaction flask, add the 250ml water dissolution, add 28 gram first seleno acetaldehyde, in 80 ℃ of reactions 2 hours, be chilled to room temperature, add concentrated hydrochloric acid 100ml, reacted 1 hour down at 85 ℃, get first seleno methylhydantoi 33 grams, yield 78%.
(5) preparation of methylselenocysteinefrom salt: in 100ml 20% sodium hydroxide solution, add 21 gram first seleno methylhydantois, 100 ℃ of following stirring and refluxing 24 hours, methylselenocysteinefrom salt.
(6) preparation of methylselenocysteinefrom: with methylselenocysteinefrom salt with hcl acidifying to pH 5-6, separate out methylselenocysteinefrom 12 gram, yield 65%.
Embodiment 2:
(1) dimethyl diselenide ether (CH
3SeSeCH
3) preparation: method is with embodiment 1;
(2) methyl-hydroselenide potassium (CH
3SeK) preparation: 50 gram dimethyl diselenide ethers are dissolved among 20 milliliters of DMF, add 100 milliliters of 30% potassium hydroxide solutions under stirring, solution is cooled to 5-10 ℃, and keep temperature to be lower than 10 ℃, slowly add sodium borohydride 6 grams in batches, after adding solution is incubated 2 hours in 40-45 ℃.The pressure reducing and steaming solvent is separated out white solid methyl-hydroselenide potassium 58 grams, yield 82%.；
(3) first seleno acetaldehyde (CH
3SeCH
2CHO) preparation: in there-necked flask, add 70 gram monochloroacetaldehydes (40% aqueous solution) and 40 gram methyl-hydroselenide potassium, 40 ℃ of following stirring and refluxing 3 hours, first seleno acetaldehyde 33 restrains yield 80%.
(4) preparation of first seleno methylhydantoi: get 30 gram volatile salts, 9 gram sodium cyanides in reaction flask, add the 250ml water dissolution, add 21 gram first seleno acetaldehyde, in 70 ℃ of reactions 2 hours, be chilled to room temperature, add concentrated hydrochloric acid 100ml, reacted 1 hour down at 95 ℃, get first seleno methylhydantoi 21 grams, yield 66%.
(5) preparation of methylselenocysteinefrom salt: in 100ml 20% sodium hydroxide solution, add 18 gram first seleno methylhydantois, 80 ℃ of following stirring and refluxing 24 hours, methylselenocysteinefrom salt.
(6) preparation of methylselenocysteinefrom: with methylselenocysteinefrom salt with hcl acidifying to pH 6-7, separate out methylselenocysteinefrom 9 gram, yield 57%.
Embodiment 3:
(1) dimethyl diselenide ether (CH
3SeSeCH
3) preparation: method is with embodiment 1;
(2) sodium methyl-hydroselenide (CH
3SeNa) preparation: method is with embodiment 1.
(3) first seleno acetaldehyde (CH
3SeCH
2CHO) preparation: in there-necked flask, add 55g bromoacetaldehyde, 60 ml waters and 50g sodium methyl-hydroselenide, 90 ℃ of following stirring and refluxing 3 hours, first seleno acetaldehyde 49g, yield 83%.
(4) preparation of first seleno methylhydantoi: get 30 gram volatile salts, 9 gram sodium cyanides in reaction flask, add the 250ml water dissolution, add 21 gram first seleno acetaldehyde, in 100 ℃ of reactions 2 hours, be chilled to room temperature, add concentrated hydrochloric acid 100ml, reacted 1 hour down at 85 ℃, get first seleno methylhydantoi 24 grams, yield 75%.
(5) preparation of methylselenocysteinefrom salt: in autoclave, add 100ml 20% sodium hydroxide solution and 18 gram first seleno methylhydantois, in 160 ℃, 5kg/cm
2Pressure reacted 2 hours down, got methylselenocysteinefrom salt.
(6) preparation of methylselenocysteinefrom: with methylselenocysteinefrom salt with hcl acidifying to pH 6-7, separate out methylselenocysteinefrom 10 gram, yield 63%.。
Embodiment 4:
(1) dimethyl diselenide ether (CH
3SeSeCH
3) preparation: method is with embodiment 1;
(2) sodium methyl-hydroselenide (CH
3SeNa) preparation: method is with embodiment 1.
(3) first seleno acetaldehyde (CH
3SeCH
2CHO) preparation: in there-necked flask, add 55g bromoacetaldehyde, 60 ml waters and 50g sodium methyl-hydroselenide, 70 ℃ of following stirring and refluxing 3 hours, first seleno acetaldehyde 52g, yield 88%.
(4) preparation of first seleno methylhydantoi: get 30 gram volatile salts, 9 gram sodium cyanides in reaction flask, add the 250ml water dissolution, add 21 gram first seleno acetaldehyde, in 100 ℃ of reactions 2 hours, be chilled to room temperature, add concentrated hydrochloric acid 100ml, reacted 1 hour down at 95 ℃, get first seleno methylhydantoi 25 grams, yield 78%.
(5) preparation of methylselenocysteinefrom salt: in autoclave, add 100ml 20% sodium hydroxide solution and 18 gram first seleno methylhydantois, in 120 ℃, 3kg/cm
2Pressure reacted 2 hours down, got methylselenocysteinefrom salt.
(6) preparation of methylselenocysteinefrom: with methylselenocysteinefrom salt with hcl acidifying to pH6-7, separate out methylselenocysteinefrom 11 gram, yield 69%.
Embodiment 5:
(1) dimethyl diselenide ether (CH
3SeSeCH
3) preparation: method is with embodiment 1;
(2) sodium methyl-hydroselenide (CH
3SeNa) preparation: method is with embodiment 1.
(3) first seleno acetaldehyde (CH
3SeCH
2CHO) preparation: in there-necked flask, add 76g Jod-acetaldehyd, 60 ml waters and 50g sodium methyl-hydroselenide, 55 ℃ of following stirring and refluxing 3 hours, first seleno acetaldehyde 53g, yield 90%.
(4) preparation of first seleno methylhydantoi: get 40 gram volatile salts, 12 gram sodium cyanides in reaction flask, add the 250ml water dissolution, add 28 gram first seleno acetaldehyde, in 80 ℃ of reactions 2 hours, be chilled to room temperature, add concentrated hydrochloric acid 100ml, reacted 1 hour down at 85 ℃, get first seleno methylhydantoi 33 grams, yield 78%.
(5) preparation of methylselenocysteinefrom salt: in 100ml 20% sodium hydroxide solution, add 21 gram first seleno methylhydantois, 100 ℃ of following stirring and refluxing 24 hours, methylselenocysteinefrom salt.
(6) preparation of methylselenocysteinefrom: with methylselenocysteinefrom salt with hcl acidifying to pH 5-6, separate out methylselenocysteinefrom 12 gram, yield 65%.
Embodiment 6:
(1) dimethyl diselenide ether (CH
3SeSeCH
3) preparation: method is with embodiment 1;
(2) sodium methyl-hydroselenide (CH
3SeNa) preparation: method is with embodiment 1.
(3) first seleno acetaldehyde (CH
3SeCH
2CHO) preparation: in there-necked flask, add 30g fluorine acetaldehyde, 60 ml waters and 50g sodium methyl-hydroselenide, 70 ℃ of following stirring and refluxing 3 hours, first seleno acetaldehyde 44g, yield 75%.
(4) preparation of first seleno methylhydantoi: get 40 gram volatile salts, 12 gram sodium cyanides in reaction flask, add the 250ml water dissolution, add 28 gram first seleno acetaldehyde, in 80 ℃ of reactions 2 hours, be chilled to room temperature, add concentrated hydrochloric acid 100ml, reacted 1 hour down at 85 ℃, get first seleno methylhydantoi 33 grams, yield 78%.
(5) preparation of methylselenocysteinefrom salt: in 100ml 20% sodium hydroxide solution, add 21 gram first seleno methylhydantois, 100 ℃ of following stirring and refluxing 24 hours, methylselenocysteinefrom salt.(6) preparation of methylselenocysteinefrom: with methylselenocysteinefrom salt with hcl acidifying to pH5-6, separate out methylselenocysteinefrom 12 gram, yield 65%.
Embodiment 7:
(1) dimethyl diselenide ether (CH
3SeSeCH
3) preparation: method is with embodiment 1;
(2) methyl-hydroselenide ammonium (CH
3SeNH
4) preparation: 50 gram dimethyl diselenide ethers are dissolved among 20 milliliters of DMF, add 100 milliliters of 15% ammoniacal liquor under stirring, solution is cooled to 5-10 ℃, and keep temperature to be lower than 10 ℃, slowly add sodium borohydride 6 grams in batches, after adding solution is incubated 2 hours in 40-45 ℃.The pressure reducing and steaming solvent gets methyl-hydroselenide ammonium 42 grams, yield 65%.
(3) first seleno acetaldehyde (CH
3SeCH
2CHO) preparation: add 100g monochloroacetaldehyde (40% aqueous solution) and 50g methyl-hydroselenide ammonium in there-necked flask, 55 ℃ of following stirring and refluxing 3 hours must first seleno acetaldehyde 50g, yield 85%.
(4) preparation of first seleno methylhydantoi: get 40 gram volatile salts, 12 gram sodium cyanides in reaction flask, add the 250ml water dissolution, add 28 gram first seleno acetaldehyde, in 80 ℃ of reactions 2 hours, be chilled to room temperature, add concentrated hydrochloric acid 100ml, reacted 1 hour down at 85 ℃, get first seleno methylhydantoi 33 grams, yield 78%.
(5) preparation of methylselenocysteinefrom salt: in 100ml 20% sodium hydroxide solution, add 21 gram first seleno methylhydantois, 100 ℃ of following stirring and refluxing 24 hours, methylselenocysteinefrom salt.
(6) preparation of methylselenocysteinefrom: with methylselenocysteinefrom salt with hcl acidifying to pH5-6, separate out methylselenocysteinefrom 12 gram, yield 65%.
Claims (6)
1. one kind is passed through the method that first seleno acetaldehyde synthesizes methylselenocysteinefrom, it is characterized in that following synthesis step:
(1) with methyl-hydroselenide salt and halo acetaldehyde reaction generation first seleno acetaldehyde, described methyl-hydroselenide salt is a kind of in sodium methyl-hydroselenide, methyl-hydroselenide potassium, methyl-hydroselenide ammonium, methyl-hydroselenide lithium, methyl-hydroselenide rubidium or the methyl-hydroselenide caesium;
(2) first seleno acetaldehyde warp and volatile salt and sodium cyanide, hydrochloric acid reaction gets first seleno methylhydantoi;
(3) first seleno methylhydantoi gets methylselenocysteinefrom salt through sodium hydroxide hydrolysis;
(4) methylselenocysteinefrom salt with acidifying neutralize methylselenocysteinefrom.
2. the method by the synthetic methylselenocysteinefrom of first seleno acetaldehyde as claimed in claim 1 is characterized in that: described halo acetaldehyde is a kind of in monochloroacetaldehyde, bromoacetaldehyde, Jod-acetaldehyd or the fluorine acetaldehyde.
3. the method by the synthetic methylselenocysteinefrom of first seleno acetaldehyde as claimed in claim 1, it is characterized in that: step (1) is carried out under 40-90 ℃, and product is a first seleno acetaldehyde.
4. the method by the synthetic methylselenocysteinefrom of first seleno acetaldehyde as claimed in claim 1, it is characterized in that: step (2) is carried out under 70-100 ℃, and product is a first seleno methylhydantoi.
5. the method by the synthetic methylselenocysteinefrom of first seleno acetaldehyde as claimed in claim 1, it is characterized in that: step (3) is carried out under 80-160 ℃, and product is a methylselenocysteinefrom salt.
6. the method by the synthetic methylselenocysteinefrom of first seleno acetaldehyde as claimed in claim 1 is characterized in that: in step (4), add acid and be neutralized to pH 5-7, product is a methylselenocysteinefrom.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735130A (en) * | 2010-01-15 | 2010-06-16 | 广州九益生物技术有限公司 | Preparation method of dimethyl diselenide |
| CN102146050A (en) * | 2010-02-10 | 2011-08-10 | 王玲 | Synthesis method, racemization method and separation method of Se-methylselenocysteine |
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| CN108929254B (en) * | 2018-09-07 | 2020-04-07 | 河南省科学院化学研究所有限公司 | Synthesis method of selenium methyl selenocysteine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6794537B1 (en) * | 2002-11-07 | 2004-09-21 | Sami Labs Limited | Manufacturing processes for Se-methyl-L-selenocysteine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6794537B1 (en) * | 2002-11-07 | 2004-09-21 | Sami Labs Limited | Manufacturing processes for Se-methyl-L-selenocysteine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735130A (en) * | 2010-01-15 | 2010-06-16 | 广州九益生物技术有限公司 | Preparation method of dimethyl diselenide |
| CN102146050A (en) * | 2010-02-10 | 2011-08-10 | 王玲 | Synthesis method, racemization method and separation method of Se-methylselenocysteine |
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