CN1948282A - Method of synthesizing selenium methyl selenium substituted cysteine through methyl seleno acetaldehyde - Google Patents
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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 invention relates to a method for synthesizing amino acid medicine, in particular to a method for synthesizing selenium methyl selenocysteine by methyl seleno acetaldehyde.
Background
Selenium is a trace element necessary for human bodies, is a composition component of erythrocyte glutathione peroxidase, and has the main function of participating in enzyme synthesis and protecting the structure and the function of cell membranes from excessive oxidation and interference. Selenium deficiency causes a series of body dysfunction such as reduction of selenase activity, oxygen radical clearance obstruction, biomembrane damage, detoxification, hypoimmunity and the like, thereby causing various diseases. Selenium has anticancer, heart protecting, cataract preventing, keshan disease preventing, Kashin-Beck disease preventing, antiaging, and heavy metal toxic removing effects. At present, more than 40 countries and regions in the world are lack of selenium, and 1 hundred million people in China are lack of selenium or low in selenium, and diseases related to selenium deficiency are suffered from or are very easy to occur. For the lack of selenium, inorganic salt sodium selenite tablets or sodium selenite fortified food is commonly used for supplement in China, but the inorganic selenium has high toxicity and is forbidden or restricted to be used in many countries; organic selenium compounds such as selenoprotein are mainly used for supplement in foreign countries. The selenium methyl selenocysteine is one of the existing forms of organic selenium in selenium-rich natural food (such as selenium-rich garlic), and is a stable, efficient and safe selenium supplement component. The selenium methyl selenocysteine has the functions of resisting cancer, resisting oxidation and aging, treating cardiovascular and cerebrovascular diseases, removing heavy metal toxicity and the like, and is widely applied to the aspects of medicine, nutrition, health care, agriculture and the like. The production of natural selenium-rich food is often limited by natural conditions, and the selenium content of the product is unstable; the chemical method for synthesizing the selenium methyl selenocysteine is not limited by natural conditions, has single product component and stable and controllable quality, and is an effective way for producing selenium supplement products.
At present, the synthesis of the selenium methyl selenocysteine mainly comprises the following methods:
(1) the method of the chloropropionic acid sodium diselenide comprises the following steps: reacting chloropropionic acid with sodium diselenide to generate selenocysteine, reducing and cracking with metallic sodium/liquid ammonia (-70 ℃), and alkylating with methyl iodide to obtain selenomethylselenocysteine. The method relates to ultralow temperature and active dangerous metal sodium, has harsh reaction conditions, high requirements on process equipment, difficult source of chloropropionic acid raw materials, high cost and difficult large-scale production (Tanaka, H; Soda, K; Selenocysteine. methods enzymol., 1987, 143, 240-;
(2) the tertiary butoxy acyl protected serine method comprises the steps of reacting tertiary butoxy acyl serine with azodicarbonic diester to generate β lactone in the presence of trialkyl (aryl) phosphorus or phosphite, then reacting with methyl selenol or salt thereof to generate tertiary butoxy acyl protected selenium methyl selenocysteine, and finally removing protection to obtain the selenium methyl selenocysteine, wherein the method has the disadvantages of long process, low product yield and expensive raw material serine and protection reagent, so the production cost is high, and the large-scale production is difficult (Spallelhz, J.E.; Reid, T.W.; Walkup, R.D.; amino of using synthetic L-Se-methyl electroluminescence as a nuclear method of its synthesis, EP 1205471, 2001);
(3) the method for substituting chloropropionic acid by sodium methylselenolate comprises the following steps: and substituting chlorine in the chloropropionic acid or methyl chloropropionate by sodium methylselenolate to obtain the selenomethylselenocysteine. The method has the defects of difficult source of the chloropropionic acid raw material and high production cost, and is not beneficial to large-scale production (Majeed; Muhammed (Piscataway, NJ); Nagabhushanam; Kalyanam (North Brunswick, NJ); Manufacturing processes for Se-methyl-L-selenocystine, US 6794537B 1, 2004).
To sum up, some of the existing methods for synthesizing selenomethylselenocysteine have the defects of difficult raw material source, high price, overhigh production cost, complex process route, low yield, low product purity, harsh reaction conditions, high equipment requirement, difficult management and the like, are not beneficial to large-scale production, and are difficult to meet the increasing market demand.
Disclosure of Invention
The invention aims to provide a synthetic method of selenium methyl selenocysteine, which has the advantages of simple synthetic route, easily obtained and cheap raw materials, high yield, convenient operation and low cost and is suitable for large-scale industrial production.
The aim of the invention is realized by the following steps of the synthetic method:
(1) reacting methyl selenol salt with halogenated acetaldehyde to generate methyl seleno acetaldehyde;
(2) reacting methylselenoacetaldehyde with ammonium carbonate, sodium cyanide and hydrochloric acid to obtain methylselenoacyl lactoyl urea;
(3) hydrolyzing methylselenocylhydantoin with sodium hydroxide to obtain selenomethylselenocysteine salt;
(4) the selenomethylselenocysteine salt is acidified and neutralized by acid (such as hydrochloric acid and the like) to obtain the selenomethylselenocysteine.
The specific implementation steps are as follows:
(1) dimethyl diselenide (CH)3SeSeCH3) The preparation of (1): in a sodium hydroxide aqueous solution, selenium powder reacts with hydrazine hydrate to generate sodium selenide, and then the sodium selenide reacts with methyl iodide or dimethyl sulfate to generate dimethyl diselenide, wherein the reaction equation is as follows:
x ═ I or OSO2OCH3；
(2) Methaneselenolate (CH)3Preparation of SeM): reacting DMF (N, N-dimethylformamide) solution of dimethyl diselenide, alkaline aqueous solution (sodium hydroxide, potassium hydroxide or ammonia water and the like) and sodium borohydride to generate methyl selenol salt, wherein the reaction equation is as follows:
M＝Na、K、NH4cations such as Li, Rb, Cs, etc.;
(3) methylselenoaldehyde (CH)3SeCH2CHO) preparation: reacting methyl selenol salt (such as sodium methyl selenol or potassium methyl selenol) with haloacetaldehyde (such as chloroacetaldehyde or bromoacetaldehyde) to generate methyl seleno acetaldehydeThe equation is as follows:
M＝Na、K、NH4cations such as Li, Rb and Cs, and halogens such as X ═ Cl, Br, I and F;
(4) preparation of methylselenomethylureides: dissolving methylselenoaldehyde, ammonium carbonate and sodium cyanide in water, heating to react, cooling to room temperature, adding concentrated hydrochloric acid, and heating to react to obtain methylselenoaldehyde ureide;
(5) preparation of selenomethylselenocysteine salt: adding methylselenomethylureide into sodium hydroxide solution, heating, refluxing and hydrolyzing to obtain selenium methyl selenocysteine sodium;
(6) preparation of selenomethylselenocysteine: acidifying the selenium methyl selenocysteine sodium with hydrochloric acid to obtain the selenium methyl selenocysteine.
The methyl selenol salt is one of sodium methyl selenol, potassium methyl selenol, ammonium methyl selenol, lithium methyl selenol, rubidium methyl selenol or cesium methyl selenol, and the halogenated acetaldehyde is one of chloroacetaldehyde, bromoacetaldehyde, iodoacetaldehyde or fluoroacetaldehyde.
The hydantoin method is one of the main methods for producing amino acid by chemical synthesis in the industry at present, and the method has low cost and high yield, and is widely used for producing amino acid at home and abroad. Aldehyde is an important intermediate for producing amino acid by a hydantoin method, and the production of selenium methyl selenocysteine by the hydantoin method can be realized by synthesizing an important intermediate methylselenoacetaldehyde. The invention generates methylselenoacetaldehyde by reacting methylselenoalkoxide (such as sodium salt or potassium salt) with haloacetaldehyde (such as chloroacetaldehyde or bromoacetaldehyde), then prepares methylselenoacetamide by utilizing the methylselenoacetaldehyde, and finally prepares the selenium methylselenocysteine by the methylselenoacetamide. The method has the advantages of simple synthetic route, convenient operation, easily available and cheap raw materials, high yield, low cost and the like, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but it should be understood that the scope of the present invention is not limited to these examples.
Example 1:
(1) dimethyl diselenide (CH)3SeSeCH3) The preparation (namely preparing the dimethyl diselenide by the conventional process) of (1): adding 500ml of water and 80g of sodium hydroxide into a three-mouth bottle with a dropping funnel and stirring, and adding 158g of selenium powder under stirring; cooling the mixture to below room temperature in a cold water bath, slowly dropwise adding 125g and 80% hydrazine hydrate for about 30min, stirring and reacting for 2 hours at 25-32 ℃, then dropwise adding 284g of methyl iodide while stirring at about 20 ℃, stirring and reacting for about 1 hour, standing and layering, separating a lower layer, and washing to obtain 141 g of orange oily dimethyl diselenide, wherein the yield is 75%;
(2) methaneselenol sodium (CH)3SeNa) (namely, preparing sodium methylselenolate by a conventional process): dissolving 50g of dimethyl diselenide in 20 ml of DMF, adding 100ml of 20% sodium hydroxide solution under stirring, cooling the solution to 5-10 ℃, keeping the temperature below 10 ℃, slowly adding 6g ofsodium borohydride in batches, and after the addition, keeping the temperature of the solution at 40-45 ℃ for 2 hours. The solvent was evaporated under reduced pressure to precipitate 52g of white solid sodium methylselenolate with a yield of 84%.
(3) Methylselenoaldehyde (CH)3SeCH2CHO) preparation: 100g chloroacetaldehyde (40%Aqueous solution) and 50g of sodium methylselenoate, stirring and refluxing for 3 hours at 55 ℃ to obtain 50g of methylselenoacetaldehyde with the yield of 85 percent.
(4) Preparation of methylselenomethylureides: 40 g of ammonium carbonate and 12 g of sodium cyanide are taken to be put into a reaction bottle, 250ml of water is added for dissolving, 28 g of methylselenoacetaldehyde is added for reacting for 2 hours at the temperature of 80 ℃, the mixture is cooled to the room temperature, 100ml of concentrated hydrochloric acid is added for reacting for 1 hour at the temperature of 85 ℃, 33 g of methylselenoacyl lactoyl urea is obtained, and the yield is 78%.
(5) Preparation of selenomethylselenocysteine salt: adding 21 g of methylselenocylhydantoin into 100ml of 20% sodium hydroxide solution, and stirring and refluxing for 24 hours at 100 ℃ to obtain the selenomethylselenocysteine.
(6) Preparation of selenomethylselenocysteine: the selenium methyl selenocysteine salt is acidified to pH5-6 with hydrochloric acid, 12 g of selenium methyl selenocysteine is separated out, and the yield is 65%.
Example 2:
(1) dimethyl diselenide (CH)3SeSeCH3) The preparation of (1): the procedure is as in example 1;
(2) potassium methyl selenol (CH)3SeK) preparation: dissolving 50g of dimethyl diselenide into 20 ml of DMF, adding 100ml of 30% potassium hydroxide solution under stirring, cooling the solution to 5-10 ℃, keeping the temperature below 10 ℃, slowly adding 6g of sodium borohydride in batches, and after the solution is added, keeping the temperature at 40-45 ℃ for 2 hours. The solvent was evaporated under reduced pressure to precipitate 58g of white solid potassium methylselenolate with a yield of 82%. (ii) a
(3) Methylselenoaldehyde (CH)3SeCH2CHO) preparation: 70 g of chloroacetaldehyde (40% aqueous solution) and 40 g of potassium methoxide were added into a three-necked flask, and the mixture was stirred and refluxed at 40 ℃ for 3 hours to obtain 33 g of methylselenoacetaldehyde with a yield of 80%.
(4) Preparation of methylselenomethylureides: 30g of ammonium carbonate and 9g of sodium cyanide are taken to be put into a reaction bottle, 250ml of water is added for dissolving, 21 g of methylselenoacetaldehyde is added for reacting for 2 hours at 70 ℃, the mixture is cooled to room temperature, 100ml of concentrated hydrochloric acid is added for reacting for 1 hour at 95 ℃, 21 g of methylselenoacyl lactoyl urea is obtained, and the yield is 66%.
(5) Preparation of selenomethylselenocysteine salt: adding 18 g of methylselenomethyllactonuride into 100ml of 20% sodium hydroxide solution, and stirring and refluxing for 24 hours at 80 ℃ to obtain the selenomethylselenocysteine.
(6) Preparation of selenomethylselenocysteine: the selenium methyl selenocysteine salt is acidified to pH6-7 by hydrochloric acid, 9g of selenium methyl selenocysteine is separated out, and the yield is 57%.
Example 3:
(1) dimethyl diselenide (CH)3SeSeCH3) The preparation of (1): the procedure is as in example 1;
(2) methaneselenol sodium (CH)3Sera) preparation: the procedure is as in example 1.
(3) Methylselenoaldehyde (CH)3SeCH2CHO) preparation: adding into a three-mouth bottle55g of bromoacetaldehyde, 60 ml of water and 50g of sodium methylselenolate are stirred and refluxed for 3 hours at the temperature of 90 ℃ to obtain 49g of methylselenoacetaldehyde with the yield of 83 percent.
(4) Preparation of methylselenomethylureides: 30g of ammonium carbonate and 9g of sodium cyanide are taken to be put into a reaction bottle, 250ml of water is added for dissolving, 21 g of methylselenoacetaldehyde is added for reacting for 2 hours at the temperature of 100 ℃, the mixture is cooled to the room temperature, 100ml of concentrated hydrochloric acid is added for reacting for 1 hour at the temperature of 85 ℃, 24 g of methylselenoacyl lactoyl urea is obtained, and the yield is 75%.
(5) Preparation of selenomethylselenocysteine salt: 100ml of 20% sodium hydroxide solution and 18 g of methylselenomethylureide were placed in an autoclave at 160 ℃ and 5kg/cm2Reacting for 2 hours under pressure to obtain the selenomethylselenocysteine salt.
(6) Preparation of selenomethylselenocysteine: the selenium methyl selenocysteine salt is acidified to pH6-7 by hydrochloric acid, 10 g of selenium methyl selenocysteine is separated out, and the yield is 63%. .
Example 4:
(1) dimethyl diselenide (CH)3SeSeCH3) The preparation of (1): the procedure is as in example 1;
(2) methaneselenol sodium (CH)3Sera) preparation: the procedure is as in example 1.
(3) Methylselenoaldehyde (CH)3SeCH2CHO) preparation: adding 55g of bromoacetaldehyde, 60 ml of water and 50g of sodium methylselenolate into a three-necked flask, and stirring and refluxing for 3 hours at 70 ℃ to obtain 52g of methylselenoacetaldehyde with the yield of 88%.
(4) Preparation of methylselenomethylureides: 30g of ammonium carbonate and 9g of sodium cyanide are taken to be put into a reaction bottle, 250ml of water is added for dissolving, 21 g of methylselenoacetaldehyde is added for reacting for 2 hours at the temperature of 100 ℃, the mixture is cooled to the room temperature, 100ml of concentrated hydrochloric acid is added for reacting for 1 hour at the temperature of 95 ℃, 25g of methylselenoacyl lactoyl urea is obtained, and the yield is 78%.
(5) Preparation of selenomethylselenocysteine salt: 100ml of 20% sodium hydroxide solution and 18 g of methylselenomethylureide were placed in an autoclave at 120 ℃ and 3kg/cm2Reacting for 2 hours under pressure to obtain the selenomethylselenocysteine salt.
(6) Preparation of selenomethylselenocysteine: the selenium methyl selenocysteine salt is acidified to pH6-7 by hydrochloric acid, 11 g of selenium methyl selenocysteine is separated out, and the yield is 69%.
Example 5:
(1) dimethyl diselenide (CH)3SeSeCH3) The preparation of (1): the procedure is as in example 1;
(2) methaneselenol sodium (CH)3Sera) preparation: the procedure is as in example 1.
(3) Methylselenoaldehyde (CH)3SeCH2CHO) preparation: 76g of iodoacetaldehyde, 60 ml of water and 50g of sodium methylselenolate are added into a three-necked flask, and stirring and refluxing are carried out for 3 hours at the temperature of 55 ℃ to obtain 53g of methylselenoacetaldehyde with the yield of 90 percent.
(4) Preparation of methylselenomethylureides: 40 g of ammonium carbonate and 12 g of sodium cyanide are taken to be put into a reaction bottle, 250ml of water isadded for dissolving, 28 g of methylselenoacetaldehyde is added for reacting for 2 hours at the temperature of 80 ℃, the mixture is cooled to the room temperature, 100ml of concentrated hydrochloric acid is added for reacting for 1 hour at the temperature of 85 ℃, 33 g of methylselenoacyl lactoyl urea is obtained, and the yield is 78%.
(5) Preparation of selenomethylselenocysteine salt: adding 21 g of methylselenocylhydantoin into 100ml of 20% sodium hydroxide solution, and stirring and refluxing for 24 hours at 100 ℃ to obtain the selenomethylselenocysteine.
(6) Preparation of selenomethylselenocysteine: the selenium methyl selenocysteine salt is acidified to pH5-6 with hydrochloric acid, 12 g of selenium methyl selenocysteine is separated out, and the yield is 65%.
Example 6:
(1) dimethyl diselenide (CH)3SeSeCH3) The preparation of (1): the procedure is as in example 1;
(2) methaneselenol sodium (CH)3Sera) preparation: the procedure is as in example 1.
(3) Methylselenoaldehyde (CH)3SeCH2CHO) preparation: 30g of fluoroacetaldehyde, 60 ml of water and 50g of sodium methylselenolate are added into a three-necked flask, and stirring and refluxing are carried out for 3 hours at 70 ℃ to obtain 44g of methylselenoacetaldehyde with the yield of 75%.
(4) Preparation of methylselenomethylureides: 40 g of ammonium carbonate and 12 g of sodium cyanide are taken to be put into a reaction bottle, 250ml of water is added for dissolving, 28 g of methylselenoacetaldehyde is added for reacting for 2 hours at the temperature of 80 ℃, the mixture is cooled to the room temperature, 100ml of concentrated hydrochloric acid is added for reacting for 1 hour at the temperature of 85 ℃, 33 g of methylselenoacyl lactoyl urea is obtained, and the yield is 78%.
(5) Preparation of selenomethylselenocysteine salt: adding 21 g of methylselenocylhydantoin into 100ml of 20% sodium hydroxide solution, and stirring and refluxing for 24 hours at 100 ℃ to obtain the selenomethylselenocysteine.
(6) Preparation of selenomethylselenocysteine: the selenium methyl selenocysteine salt is acidified to pH5-6 with hydrochloric acid, 12 g of selenium methyl selenocysteine is separated out, and the yield is 65%.
Example 7:
(1) dimethyl diselenide (CH)3SeSeCH3) The preparation of (1): the procedure is as in example 1;
(2) methaneselenolammonium (CH)3SeNH4) The preparation of (1): dissolving 50g of dimethyl diselenide into 20 ml of DMF, adding 100ml of 15% ammonia water under stirring, cooling the solution to 5-10 ℃, keeping the temperature lower than 10 ℃, slowly adding 6g of sodium borohydride in batches, and after the addition, keeping the temperature of the solution at 40-45 ℃ for 2 hours. The solvent was evaporated under reduced pressure to give 42 g of ammonium methylselenolate with a yield of 65%.
(3) Methylselenoaldehyde (CH)3SeCH2CHO) preparation: 100g chloroacetaldehyde (40% aqueous solution) and 50g sodium methylselenolate are added into a three-necked flask, and stirring and refluxing are carried out for 3 hours at the temperature of 55 ℃, so as to obtain 50g of methylselenoacetaldehyde with the yield of 85%.
(4) Preparation of methylselenomethylureides: 40 g of ammonium carbonate and 12 g of sodium cyanide are taken to be put into a reaction bottle, 250ml of water is added for dissolving, 28 g of methylselenoacetaldehyde is added for reacting for 2 hours at the temperature of 80 ℃, the mixture is cooled to the room temperature, 100ml of concentrated hydrochloric acid is added for reacting for 1 hour at the temperature of 85 ℃, 33 g of methylselenoacyl lactoyl urea is obtained, and the yield is 78%.
(5) Preparation of selenomethylselenocysteine salt: adding 21 g of methylselenocylhydantoin into 100ml of 20% sodium hydroxide solution, and stirring and refluxing for 24 hours at 100 ℃ to obtain the selenomethylselenocysteine.
(6) Preparation of selenomethylselenocysteine: the selenium methyl selenocysteine salt is acidified to pH5-6 with hydrochloric acid, 12 g of selenium methyl selenocysteine is separated out, and the yield is 65%.
Claims (7)
1. A method for synthesizing selenium methyl selenocysteine by methyl seleno acetaldehyde is characterized by comprising the following synthesis steps:
(1) reacting methyl selenol salt with halogenated acetaldehyde to generate methyl seleno acetaldehyde;
(2) reacting methylselenoacetaldehyde with ammonium carbonate, sodium cyanide and hydrochloric acid to obtain methylselenoacyl lactoyl urea;
(3) hydrolyzing methylselenocylhydantoin with sodium hydroxide to obtain selenomethylselenocysteine salt;
(4) the selenium methyl selenocysteine salt is acidified and neutralized by acid to obtain the selenium methyl selenocysteine.
2. The method of synthesizing selenomethylselenocysteine from methylselenoacetal as claimed in claim 1, wherein: the methyl selenol salt is one of sodium methyl selenol, potassium methyl selenol, ammonium methyl selenol, lithium methyl selenol, rubidium methyl selenol or cesium methyl selenol, and the halogenated acetaldehyde is one of chloroacetaldehyde, bromoacetaldehyde, iodoacetaldehyde or fluoroacetaldehyde.
3. The method of synthesizing selenomethylselenocysteine from methylselenoacetal as claimed in claim 1, wherein: comprises synthesizing the important intermediates methylselenoacetaldehyde and methylselenoamethyleneureide.
4. The method of synthesizing selenomethylselenocysteine from methylselenoacetal as claimed in claim 1, wherein: the step (1) is carried out at 40-90 ℃, and the product is methylselenoacetaldehyde.
5. The method of synthesizing selenomethylselenocysteine from methylselenoacetal as claimed in claim 1, wherein: the step (2) is carried out at 70-100 ℃, and the product is methylselenomethylureide.
6. The method of synthesizing selenomethylselenocysteine from methylselenoacetal as claimed in claim 1, wherein: the step (3) is carried out at 80-160 ℃, and the product is code methyl selenocysteine.
7. The method of synthesizing selenomethylselenocysteine from methylselenoacetal as claimed in claim 1, wherein: in step (4), acid is added to neutralize to pH5-7, and the product is selenomethylselenocysteine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102146050A (en) * | 2010-02-10 | 2011-08-10 | 王玲 | Synthesis method, racemization method and separation method of Se-methylselenocysteine |
| CN108929254A (en) * | 2018-09-07 | 2018-12-04 | 河南省科学院化学研究所有限公司 | A kind of synthetic method of methylselenocysteinefrom |
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| CN101735130A (en) * | 2010-01-15 | 2010-06-16 | 广州九益生物技术有限公司 | Method for preparing dimethyl diselenide |
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| US6794537B1 (en) * | 2002-11-07 | 2004-09-21 | Sami Labs Limited | Manufacturing processes for Se-methyl-L-selenocysteine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146050A (en) * | 2010-02-10 | 2011-08-10 | 王玲 | Synthesis method, racemization method and separation method of Se-methylselenocysteine |
| CN108929254A (en) * | 2018-09-07 | 2018-12-04 | 河南省科学院化学研究所有限公司 | A kind of synthetic method of methylselenocysteinefrom |
| 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 |
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