CN1280261C - Improved process for synthesizing L-theanine - Google Patents
Improved process for synthesizing L-theanine Download PDFInfo
- Publication number
- CN1280261C CN1280261C CN 200410033794 CN200410033794A CN1280261C CN 1280261 C CN1280261 C CN 1280261C CN 200410033794 CN200410033794 CN 200410033794 CN 200410033794 A CN200410033794 A CN 200410033794A CN 1280261 C CN1280261 C CN 1280261C
- Authority
- CN
- China
- Prior art keywords
- theanine
- reaction
- ethylamine
- present
- synthesizing
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to an improved method for synthesizing L-theanine. The synthesis and production method of the L-theanine of the present invention puts forward optimized and easily operated reaction conditions; L-pyrrolidone acid and anhyrous ethylamine react under the existence condition of antioxidants or the good environment that air is exhausted by dried ethylamine gas, and accordingly, the high-quality L-theanine can be produced. The reaction temperature is controlled from 30 to 59 DEG C; reaction pressure is from 0.4 to 5.9MPa, and product yield is obviously higher than the yield under the condition of no antioxidants or no need of dried ethylamine gas for exhausting air.
Description
Invention field
The present invention relates to organic chemistry and pharmaceutical chemistry field, particularly, the feature amino acid that the present invention relates to tealeaves is the improvement synthetic method of L-theanine.
Background technology
L-theanine (L-theanine) is for to be present in the feature amino acid of nature tealeaves and to be the L type, chemistry is by name: N-ethyl-L-glutaminate (N-ethyl-L-glutamine), U.S. chemical abstract registration number CAS:[3081-61-6], pure product are white, needle-shaped crystals, fusing point: 217-218 ℃ (decomposition), specific optical rotation: [α]
20 D:+7.7-+8.5 ° (5%, H
2O).
Its structural formula is as follows:
Because containing the L-theanine in the tealeaves only is 2%, for satisfying market demand, prepares the L-theanine with chemical synthesis and has economic implications.
As far back as nineteen forty-two Israelis N.Lichtenstein (J.Am.Chem.Soc., 1942,64,1021-1022) first in the laboratory with tetramethyleneimine ketone acid and 33% ethylamine solution reaction (37 ℃, 20 days), obtain theanine, this method yield is very low.Nineteen fifty; the wine family of Japan is two youths (Japanese agriculture chemistry meeting will more; 1950; 23:269) proposing with L-L-glutamic acid-γ-ethyl ester is raw material; behind chloroformic acid benzyl ester protection amino,, be catalysed and reduced into the L-theanine with Pd/C again with the ethylamine solution reaction; use precious metal palladium to make catalyzer, the production cost height.
Nineteen fifty-one, the bridge pawl of Japan refined (Japanese agriculture chemistry meeting will, 1951,25:25-26) improved synthetic method, promptly use L-tetramethyleneimine ketone acid and pure ethamine rather than ethylamine solution,, make the yield of theanine bring up to 43.2% in 28-32 ℃ of placing response 14-28 days.
1964, T.Furuyama (Bull.Chem.Soc.Japan, 1964,37,1078) adopted dithiocarbonic anhydride protection amino and has synthesized theanine.
Nineteen sixty-five, it is raw material that N.Lichtenstein uses L-glutamic acid acetaldehyde instead, is reduced into theanine with Pd/C, and has applied for Israel's patent (Israeli, 23768,1965).
1966, and Y.Yamada etc. (Bull.Chem.Soc.Japan, 1966,39,1999-2000) once with L-tetramethyleneimine ketone acid XianCheng mantoquita, synthesize theanine with anhydrous ethylamine in 7 days method of 70 ℃ of reactions again, yield is improved.
1997, (foodstuff additive handbook, Chemical Industry Press such as Ling Guanting, 1997,136-137) in book, point out, still adopt L-L-glutamic acid thermal dehydration to generate the tetramethyleneimine ketone acid in Japan, and then under high pressure heat with anhydrous ethylamine and theanine, but do not see detailed process and data.
The amino synthetic method of protection that relates to the L-theanine also has patent documentation as JP570491A, JP 9263573A, JP 11116542A, (fine chemistry industry, 2001,4, the articles of 223-224) delivering such as JP 2000-36383A and Wang Sanyong.
Goal of the invention
The object of the invention provides a kind of production synthetic method of L-theanine, with market raw material on sale, makes the L-theanine have the characteristics of suitability for industrialized production, and keeps the L-configuration, provides the edible and health care of people, medicinal use with low, the colory product of price.
Summary of the invention
The invention provides the L-theanine synthetic method of improvement, and through medium-scale production checking.One of improvement:
After L-tetramethyleneimine ketone acid (commercially available, roc generationization limited liability company in Mianzhu City, Sichuan produce) fed intake, the air in the closed reactor is drained back (and without rare gas element emptying) and anhydrous ethylamine reacts with dry ethamine gas;
Reaction formula is as follows:
Two of improvement: at antioxidant (for example: quinoline, ethoxyquin with L-tetramethyleneimine ketone acid and anhydrous ethylamine, vitamins C, Quercetin or butyl hydroxy anisol (BHA), perhaps their mixture) aminating reaction is carried out in the temperature pressurization in existing down, and wherein the consumption of antioxidant is the 0.5-3% (weight ratio) of L-tetramethyleneimine ketone acid.The pressurized conditions of producing is 0.4-5.9MPa, and temperature of reaction is controlled between 30-59 ℃.
Advantage of the present invention is: technological process is brief, easy to operate under pressurization, middle temperature reaction conditions, makes suitability for industrialized production feasible, keeps the L-configuration, and product quality is guaranteed, and L-theanine total recovery 〉=58.0% is better than the method for other operational paths.
The invention will be further described below by embodiment.It should be understood that the described preparation method of the embodiment of the invention is only used for illustrating the present invention, rather than limitation of the present invention, under design prerequisite of the present invention,, all belong to the scope of protection of present invention to preparation method's of the present invention simple modifications.Except as otherwise noted, the percentage ratio among the present invention is weight percentage.
Embodiment
Embodiment one
In 500L stainless steel pressure still, add 60KgL-tetramethyleneimine ketone acid and 0.6Kg ethoxyquin, closed reactor adds 200Kg liquid anhydrous ethamine, slowly heat with hot water bath, interior temperature remains on 30-59 ℃, and middling speed stirs, and pressure remains on 0.4-5.9MPa, reacted 24-72 hour, reaction finishes, and reclaims excessive ethamine, and the ethamine of recovery can be reused and feed intake.The reaction product decolorizing with activated carbon, 95% ethyl alcohol recrystallization gets elaboration 47.3Kg, yield: 58.5%, [α]
20 D+ 7.7-+8.5 ° (5%, H
2O).
Embodiment two
In 500L stainless steel pressure still, add the closed reactor of 60KgL-tetramethyleneimine ketone acid, air in the still is drained, add liquid anhydrous ethamine 190Kg again with the dry ethamine gas in the steel cylinder, slowly heat with hot water bath, interior temperature remains on 30-59 ℃, and middling speed stirs, and pressure remains on 0.4-5.9MPa, reacted 24-72 hour, reaction finishes, and reclaims excessive ethamine, and the ethamine of recovery can be reused and feed intake.The reaction product decolorizing with activated carbon, 95% ethyl alcohol recrystallization gets elaboration 46.9Kg, yield: 58.2%, [α]
20 D+ 7.7-+8.5 ° (5%, H
2O).
Claims (5)
1, a kind of improvement synthetic method of producing the L-theanine, this method are to drain air reaction production L-theanine with L-tetramethyleneimine ketone acid and anhydrous ethylamine in the presence of antioxidant or with exsiccant ethamine gas:
2, basis the process of claim 1 wherein that adding antioxidant is selected from quinoline, ethoxyquin, vitamins C, Quercetin or butyl hydroxy anisol, perhaps their mixture.
3, according to the method for claim 2, wherein the consumption of antioxidant is the 0.5-3 weight % of L-tetramethyleneimine ketone acid.
4, according to the method for one of claim 1-3, wherein temperature of reaction is to carry out between 30-59 ℃.
5, according to the method for claim 4, wherein reaction pressure is controlled between the 0.4-5.9MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410033794 CN1280261C (en) | 2004-04-20 | 2004-04-20 | Improved process for synthesizing L-theanine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410033794 CN1280261C (en) | 2004-04-20 | 2004-04-20 | Improved process for synthesizing L-theanine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1690046A CN1690046A (en) | 2005-11-02 |
| CN1280261C true CN1280261C (en) | 2006-10-18 |
Family
ID=35345844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410033794 Expired - Fee Related CN1280261C (en) | 2004-04-20 | 2004-04-20 | Improved process for synthesizing L-theanine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1280261C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315787C (en) * | 2004-06-12 | 2007-05-16 | 郑国斌 | Preparation method of theanine |
| CN101085745A (en) * | 2006-06-09 | 2007-12-12 | 南京莱尔生物化工有限公司 | Modified synthesis method for L-theanine |
| CN101468955B (en) * | 2008-07-24 | 2012-04-18 | 宁波市镇海海德生化科技有限公司 | Production method of N-acetyl-L-glutamine |
-
2004
- 2004-04-20 CN CN 200410033794 patent/CN1280261C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1690046A (en) | 2005-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105777535B (en) | Process for preparing glucaric acid | |
| CN112279825B (en) | Preparation method of 5-halogenated methyl furfural | |
| CN107602661B (en) | Preparation method of polaprezinc | |
| CN1280261C (en) | Improved process for synthesizing L-theanine | |
| JP2937083B2 (en) | Preparation of aromatic cyanomethylamine | |
| CN101085745A (en) | Modified synthesis method for L-theanine | |
| HU224529B1 (en) | Method for the production of adrenaline | |
| CN111778297A (en) | Improved synthesis method of 1-benzyl-3-piperidinol intermediate | |
| CN109694359B (en) | Synthetic method of nitrofuran metabolite-furazolidone AOZ-D4 | |
| CN101186587A (en) | Method for synthesizing derivative of beta-amino acid and intermediate product thereof | |
| CA2329210C (en) | Process for preparation of enantiomerically pure n-methyl-n-[(1s)-1-phenyl-2((3s)-3-hydroxypyrrolidin-1-yl) ethyl]-2,2-diphenylacetamide | |
| CN1046272C (en) | Process for producing N-tert-butyl-2-pyrazinecarboxamide and N-tert-butyl-2-piperazinecarboxamide | |
| CN108602758B (en) | Process for preparing trans-4-amino-1-cyclohexanecarboxylic acids and derivatives thereof | |
| TW461884B (en) | Process to continuously prepare an aqueous mixture of ε-caprolactam and ε-caprolactam precursors | |
| CN1169782C (en) | Method for synthesizing theanine | |
| CN102127093B (en) | Refining process for Cefotiam hexetil hydrochloride | |
| CN113402420A (en) | 2-amino, 2-cyanoacetic acid methyl ester/ethyl ester, 2-amino, 2-cyanoacetic acid and synthesis process thereof | |
| JPH0768163B2 (en) | Process for producing cyclopentenone derivative | |
| CN106187799B (en) | A method of preparing DL-lysine hydrochloride | |
| CN101675055A (en) | The method for transformation of Sorbitol Powder | |
| Frye Jr et al. | 17. Catalytic Preparation of Pyrrolidones from Renewable Resources | |
| Bensalah et al. | Solvent-and catalyst-free transamidations of unprotected glycosyl carboxamides | |
| CN106946731B (en) | A kind of synthetic method of trifluoroacetyl aniline derivative | |
| CN113248407A (en) | Multifunctional aromatic amine compound and preparation method and application thereof | |
| CN102731419A (en) | Method for synthesizing carbamyl benzotriazole by three-component one-pot method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Laier Biological Chemical Co., Ltd., Nanjing Document name: Notification of Termination of Patent Right |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061018 Termination date: 20100420 |