CN105399642A - Method for simultaneously preparing D-tert-leucine and L-tert-leucine - Google Patents
Method for simultaneously preparing D-tert-leucine and L-tert-leucine Download PDFInfo
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- CN105399642A CN105399642A CN201511001905.1A CN201511001905A CN105399642A CN 105399642 A CN105399642 A CN 105399642A CN 201511001905 A CN201511001905 A CN 201511001905A CN 105399642 A CN105399642 A CN 105399642A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B57/00—Separation of optically-active compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/04—Alpha- or beta- amino acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention discloses a method for simultaneously preparing D-tert-leucine and L-tert-leucine. The method comprises the following steps: 1, reacting n-butanol with 1,1-dichloroethylene to obtain a 3,3-dimethylbutyric acid product; 2, adding a catalyst to the 3,3-dimethylbutyric acid product, introducing air and chlorine, and carrying out a chlorination reaction to obtain 2-chloro-3,3-dimethylbutyric acid; 3, carrying out an aminolysis reaction on 2-chloro-3,3-dimethylbutyric acid to obtain D, L-tert-leucine; 4, carrying out acetylation and chloroacetylation on the obtained D, L-tert-leucine, and using L-thermal stability amino acid acylase splitting and other treatments to respectively obtain D-tert-leucine and L-tert-leucine; and 5, racemizing acetylated and chloroacetylated D-tert-leucine recovered after splitting, and carrying out cycle splitting. N-butanol and 1,1-dichloroethylene with low cost are used as initial raw materials. The cost of the method is substantially lower than that of a biological reduction method.
Description
Technical field
The invention belongs to biocatalysis field, particularly a kind of method simultaneously preparing D-and L-type Terleu.
Background technology
S-Leucine and D-Terleu are very important alpha-non-natural amino acids, are the intermediates of multi-medicament.Because its side chain is a tertiary butyl, have very large sterically hindered, be conducive to maintaining space conformation after being coupled with other molecule, the amido linkage simultaneously formed is not easy the enzyme identification degraded in body.Current synthesis S-Leucine and D-Terleu, except chemical resolution method, the industrial method of biocatalysis mainly with tertiary butyl ketone acid for substrate, carry out biological reducing ammonia process with desaturase to carry out, as a kind of " method preparing S-Leucine " 201110202325 and " a kind of biocatalysis preparation method of D-Terleu " CN104513839A.There is bibliographical information immobilization sistomycocin acylase, split the DL Terleu of acidylate, but shown by the experiment of contriver; immobilization sistomycocin acylase, the concentration of substrate of tolerance is lower, more than 200mM almost non-activity; after using secondary, activity extremely significantly declines.Patent " continuous enzymatic method for producing L-tert-leucine " 201010622182; adopt phenylacetyl to modify DL Terleu; split in room temperature with immobilized Amano acylase; enzyme dependence on import; solubleness is lower at ambient temperature for the Terleu of phenylacetyl modification, and technique is unfavorable to production.
Summary of the invention
The object of this invention is to provide one and prepare DL D-, the method for S-Leucine.The invention provides a kind of method simultaneously preparing D-type Terleu and L-type Terleu in addition, its comprehensive cost of above-mentioned preparation method is significantly lower than biological reducing method for transformation.
The present invention includes following content:
One prepares DL D-, and the method for L-type Terleu, comprises the following steps:
Step (1): propyl carbinol and vinylidene chloride are reacted, obtains 3,3-dimethyl butyrate acid product;
Step (2): add catalyzer in 3,3-dimethyl butyrate acid product, pass into air and chlorine simultaneously, carry out chloro, obtains chloro-3, the 3-acid dimethyls of 2-;
Step (3): chloro-for the 2-obtained 3,3-acid dimethyls are carried out ammonolysis reaction, finally obtains DL D-, S-Leucine.
Prepare a method for D-Terleu and S-Leucine simultaneously, it is characterized in that: comprise the following steps:
Step (1): propyl carbinol and vinylidene chloride are reacted, obtains 3,3-dimethyl butyrate acid product;
Step (2): add catalyzer in 3,3-dimethyl butyrate acid product, pass into air and chlorine simultaneously, carry out chloro, obtains chloro-3, the 3-acid dimethyls of 2-;
Step (3): chloro-for the 2-obtained 3,3-acid dimethyls are carried out ammonolysis reaction, obtains DL D-, S-Leucine;
Step (4): with the DL D-described in Acetyl Chloride 98Min. or chloroacetyl chloride modification step (3), S-Leucine, to the acetylize D obtained, the D of S-Leucine or chloroacetylation, S-Leucine utilizes L-L-Aminoacylase to split;
Step (5): go split the D-Terleu reclaiming acetylizad D-Terleu or the chloroacetylation obtained to acidylate, crystallization obtains D-Terleu; Carry out racemization by splitting the D-Terleu reclaiming acetylizad D-Terleu or the chloroacetylation obtained, then split with L-L-Aminoacylase, obtain S-Leucine.The present invention is owing to have employed the propyl carbinol of low cost and vinylidene chloride as starting raw material, and the D-obtained and S-Leucine cost are far below biological reducing method for transformation.
Further, L-L-Aminoacylase is the thermally-stabilised L-Aminoacylase of L-.Preparation method about the thermally-stabilised L-Aminoacylase of L-can see AthermostableL-aminoacylasefromThermococcuslitoralis:clo ning; overexpression; characterization, andapplicationsinbiotransformations.Extremophiles.2002Ap r; 6 (2): 111-122.
The present invention overcomes the low deficiency of phenyl derivatives acidylate Terleu solubleness, adopts Acetyl Chloride 98Min. or derivatives thereof to modify Terleu, avoid phenyl import to acidylate Terleu dissolve unfavorable.Adopt the thermally-stabilised L-Aminoacylase of L-to split at relatively high temperatures simultaneously, improve the solubleness of acidylate Terleu further, high efficiency biocatalysis can be realized.
Owing to modifying D-with chloroacetyl chloride, S-Leucine, and at a higher temperature, as 70-80 DEG C, split with the thermally-stabilised L-Aminoacylase of L-, effectively add the concentration of substrate, achieve high-level efficiency and split.
As preferably, when propyl carbinol and vinylidene chloride react, the temperature of reaction system is at 0-2 DEG C, and the reaction times is 3 hours.
As preferably, step (2) adds catalyzer in 3,3-dimethyl butyrate acid product, and described catalyzer is red phosphorus.
The present invention also provides a kind of method preparing S-Leucine, comprises the following steps:
Step (1): propyl carbinol and vinylidene chloride are reacted, obtains 3,3-dimethyl butyrate acid product;
Step (2): add catalyzer in 3,3-dimethyl butyrate acid product, pass into air and chlorine simultaneously, carry out chloro, obtains chloro-3, the 3-acid dimethyls of 2-;
Step (3): chloro-for the 2-obtained 3,3-acid dimethyls are carried out ammonolysis reaction, obtains DL D-, S-Leucine;
Step (4): with the DL D-described in Acetyl Chloride 98Min. or chloroacetyl chloride modification step (3), S-Leucine, to the acetylize D obtained, the D of S-Leucine or chloroacetylation, S-Leucine utilizes L-L-Aminoacylase, splits;
Step (5): carry out racemization by splitting the D-Terleu reclaiming acetylizad D-Terleu or the chloroacetylation obtained, then split with L-L-Aminoacylase, obtain S-Leucine.
Beneficial effect of the present invention is: the present invention can prepare the chirality Terleu of two kinds of configurations simultaneously, and from economic benefit, cost significantly prepares D-and S-Leucine respectively lower than by biological reducing method.The price of D-Terleu is 3 times of S-Leucine in the market.The market scale of S-Leucine is much larger than D-Terleu.The chloroacetyl chloride D-Terleu reclaimed after enzyme catalysis can be carried out racemization by the present invention, and recirculation splits, and can have to S-Leucine.Due to synthesis D-and S-Leucine cost very low, its comprehensive cost is still lower than biological reducing method for transformation.
Embodiment
Illustrate the present invention with embodiment below, but do not limit the present invention in any form.
Embodiment 1:
1 liter of (10.9 moles) propyl carbinol is dissolved in 2.3 liters of vitriol oils, under the condition of about 0 DEG C, slowly drips vinylidene chloride 964ml(12 mole), in reaction process, the temperature controlling reaction system, at 0-2 DEG C, dropwises, reacts 3 hours.Fallen on trash ice by reaction solution, with 4 liters of normal hexane extraction products three times, recycling design, product concentrated hydrochloric acid hydrolysis, uses benzene extraction product, and recycling design obtains 3,3-acid dimethyl (1.14 kilograms, 90% yield).Product is added a small amount of red phosphorus and do catalytic reagent, at 130 DEG C, pass into air and chlorine simultaneously, react completely, blowing air is rushed unnecessary chlorine, underpressure distillation (collecting 102-109 DEG C/1mmHg), obtain chloro-3, the 3-acid dimethyls of 2-(1.31 kilograms, 89% yield), chloro thing is dissolved in strong aqua (13M), and 50 DEG C of insulations 16 hours, Liquid Detection was amino close to complete (being less than 2%), rush after unnecessary ammonia, concentrated dry, with acetic acid at 100 DEG C of Dissolved Amino Acids, cross and filter ammonium chloride.Distillation recovery acetic acid, obtains D, S-Leucine (1.06 kilograms, 93% yield).
Example 2
The Terleu of DL is water-soluble, adds sodium hydroxide and is adjusted to pH=10, and control temperature, at 0 DEG C, slowly drips Acetyl Chloride 98Min., and sodium hydroxide control pH, does not develop the color until reaction solution triketohydrindene hydrate detects simultaneously.Add salt acid for adjusting pH to 1, acetylize D, S-Leucine product becomes crystal and separates out, collecting by filtration.
Example 3
The Terleu of DL is water-soluble, adds sodium hydroxide and is adjusted to pH=10, and control temperature, at 0 DEG C, slowly drips chloroacetyl chloride, and sodium hydroxide control pH, does not develop the color until reaction solution triketohydrindene hydrate detects simultaneously.Add salt acid for adjusting pH to 1, chloroacetylation D, S-Leucine product becomes crystal and separates out, collecting by filtration.
Example 4
By acetylize D; S-Leucine is mixed into a certain amount of water; adding sodium hydroxide regulates pH to 7.5, and add Sodium phosphate dibasic and the potassium primary phosphate of solid, after dissolving, phosphatic concentration is 100mM; pH controls 7.5; be warmed up to 75 DEG C, make acetylizad D, S-Leucine dissolves completely; concentration can reach 1.2M, and optimizing the concentration of substrate split is 1M.Add the thermally-stabilised acylase of L-of the restructuring of suitable amount, at 75 DEG C of process 16-24 hour, follow the tracks of by liquid phase, until reaction proceeds to 98%.Add hydrochloric acid, regulate pH to 1, acetylize D-Terleu and a small amount of acetylizad S-Leucine do not reacted completely is precipitated gets off, collecting by filtration crystal.S-Leucine in solution, concentrated crystallization, purity is 99%, EE value more than 99%.Be mixed with the acetylizad D-Terleu of a small amount of acetylize S-Leucine, be dissolved in concentrated hydrochloric acid, boil and spend the night, remove ethanoyl at 100 DEG C, neutralization, concentrated crystallization, the purity of Crystallization Process control D-Terleu and EE value are all more than 99%.A small amount of D in mother liquor, S-Leucine reclaims, and can be used for acetylize again, carries out circulation and splits.
Example 5
By chloroacetylation D; S-Leucine is mixed into a certain amount of water; adding sodium hydroxide regulates pH to 7.5; add Sodium phosphate dibasic and the potassium primary phosphate of solid; after dissolving, phosphatic concentration is 100mM; pH controls 7.5, is warmed up to 75 DEG C, makes the D of chloroacetylation; S-Leucine dissolves completely; concentration can reach 1.1M, preferred 900mM, add appropriate restructuring the thermally-stabilised L-Aminoacylase of L (consumption be above-mentioned ethanoyl modify D-; S-Leucine 1/5th); at 75 DEG C of process 16-24 hour, follow the tracks of by liquid phase, until reaction proceeds to 98%.Add hydrochloric acid, regulate pH to 1, chloroacetylation D-Terleu and the S-Leucine of a small amount of chloroacetylation do not reacted completely is precipitated gets off, collecting by filtration crystal.Neutralized by solution, concentrated crystallization, obtains purity and EE value is greater than more than 99% S-Leucine.Be mixed with the D-Terleu of the chloroacetylation of a small amount of chloroacetylation S-Leucine, be dissolved in concentrated hydrochloric acid, boil and spend the night, remove chloracetyl at 100 DEG C, neutralization, condensing crystal, Crystallization Process control D-Terleu purity and EE value are all more than 99%.A small amount of D in mother liquor, S-Leucine reclaims, then chloroacetylation, carries out circulation and splits.
Example 6
Split the chloroacetylation D-Terleu reclaimed containing a small amount of chloroacetylation S-Leucine above; get 500 grams; be dissolved in the solution of acetic anhydride of 1.8 liters of acetic acid and 560ml; at 120 DEG C of process 30-40 minute, racemization is carried out, after reaching complete racemization to the D-Terleu of chloroacetylation; underpressure distillation; remove solvent, obtain the D of racemization, L-chloroacetylation Terleu.
More than show and describe principal character of the present invention and advantage.The technician of the industry should understand, and the present invention is not restricted to the described embodiments, and without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.
Claims (7)
1. prepare a DL D-, the method for L-type Terleu, is characterized in that: comprise the following steps:
Step (1): propyl carbinol and vinylidene chloride are reacted, obtains 3,3-dimethyl butyrate acid product;
Step (2): add catalyzer in 3,3-dimethyl butyrate acid product, pass into air and chlorine simultaneously, carry out chloro, obtains chloro-3, the 3-acid dimethyls of 2-;
Step (3): chloro-for the 2-obtained 3,3-acid dimethyls are carried out ammonolysis reaction, obtains DL D-, S-Leucine.
2. prepare a method for D-Terleu and S-Leucine simultaneously, it is characterized in that: comprise the following steps:
Step (1): propyl carbinol and vinylidene chloride are reacted, obtains 3,3-dimethyl butyrate acid product;
Step (2): add catalyzer in 3,3-dimethyl butyrate acid product, pass into air and chlorine simultaneously, carry out chloro, obtains chloro-3, the 3-acid dimethyls of 2-;
Step (3): chloro-for the 2-obtained 3,3-acid dimethyls are carried out ammonolysis reaction, obtains DL D-, S-Leucine;
Step (4): with the DL D-described in Acetyl Chloride 98Min. or chloroacetyl chloride modification step (3), S-Leucine, to the acetylize D obtained, the D of S-Leucine or chloroacetylation, S-Leucine utilizes L-L-Aminoacylase to split;
Step (5): go split the D-Terleu reclaiming acetylizad D-Terleu or the chloroacetylation obtained to acidylate, crystallization obtains D-Terleu; Carry out racemization by splitting the D-Terleu reclaiming acetylizad D-Terleu or the chloroacetylation obtained, then split with L-L-Aminoacylase, obtain S-Leucine.
3. a kind of method simultaneously preparing D-Terleu and S-Leucine according to claim 2, it is characterized in that: the propyl carbinol described in step (1) and described 1,1-Ethylene Dichloride reacts, and the temperature of reaction system is at 0-2 DEG C, and the reaction times is 3 hours.
4. a kind of method simultaneously preparing D-Terleu and S-Leucine according to claim 2, is characterized in that: described in step (2), catalyzer is red phosphorus.
5. a kind of method simultaneously preparing D-Terleu and S-Leucine according to claim 2, is characterized in that: at 70-80 DEG C, utilize L-L-Aminoacylase to split.
6. a kind of method simultaneously preparing D-Terleu and S-Leucine according to claim 2, is characterized in that: described L-L-Aminoacylase is the thermally-stabilised L-Aminoacylase of L-.
7. prepare a method for S-Leucine, it is characterized in that: comprise the following steps:
Step (1): propyl carbinol and vinylidene chloride are reacted, obtains 3,3-dimethyl butyrate acid product;
Step (2): add catalyzer in 3,3-dimethyl butyrate acid product, pass into air and chlorine simultaneously, carry out chloro, obtains chloro-3, the 3-acid dimethyls of 2-;
Step (3): chloro-for the 2-obtained 3,3-acid dimethyls are carried out ammonolysis reaction, obtains DL D-, S-Leucine;
Step (4): with the DL D-described in Acetyl Chloride 98Min. or chloroacetyl chloride modification step (3), S-Leucine, to the acetylize D obtained, the D of S-Leucine or chloroacetylation, S-Leucine utilizes L-L-Aminoacylase, splits;
Step (5): carry out racemization by splitting the D-Terleu reclaiming acetylizad D-Terleu or the chloroacetylation obtained, then split with L-L-Aminoacylase, obtain S-Leucine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503531A (en) * | 2018-04-28 | 2018-09-07 | 江苏八巨药业有限公司 | A kind of preparation method of 3,3- dimethyl-2-oxo-butyric acids |
| CN114634955A (en) * | 2022-04-22 | 2022-06-17 | 金达威生物技术(江苏)有限公司 | Method for preparing L-tert-leucine through biological enzyme catalysis and application thereof |
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| JPH1072419A (en) * | 1996-06-28 | 1998-03-17 | Sumitomo Chem Co Ltd | Production of tertiary-leucine |
| CN101570477A (en) * | 2009-06-10 | 2009-11-04 | 江苏联化科技有限公司 | Method for synthesizing 3,3-dimethylbutyrylchloride |
| CN101886110A (en) * | 2010-06-28 | 2010-11-17 | 浙江树人大学 | New method for splitting photoactive tert-leucine |
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2015
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Patent Citations (3)
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| JPH1072419A (en) * | 1996-06-28 | 1998-03-17 | Sumitomo Chem Co Ltd | Production of tertiary-leucine |
| CN101570477A (en) * | 2009-06-10 | 2009-11-04 | 江苏联化科技有限公司 | Method for synthesizing 3,3-dimethylbutyrylchloride |
| CN101886110A (en) * | 2010-06-28 | 2010-11-17 | 浙江树人大学 | New method for splitting photoactive tert-leucine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503531A (en) * | 2018-04-28 | 2018-09-07 | 江苏八巨药业有限公司 | A kind of preparation method of 3,3- dimethyl-2-oxo-butyric acids |
| CN108503531B (en) * | 2018-04-28 | 2021-02-26 | 江苏八巨药业有限公司 | Preparation method of 3, 3-dimethyl-2-oxobutyric acid |
| CN114634955A (en) * | 2022-04-22 | 2022-06-17 | 金达威生物技术(江苏)有限公司 | Method for preparing L-tert-leucine through biological enzyme catalysis and application thereof |
| CN114634955B (en) * | 2022-04-22 | 2023-07-18 | 金达威生物技术(江苏)有限公司 | Method for preparing L-tertiary leucine by biological enzyme catalysis and application thereof |
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Application publication date: 20160316 |