CN1603309A - Process for cascade reaction preparation of N-acetyl-DL-tryptophan - Google Patents
Process for cascade reaction preparation of N-acetyl-DL-tryptophan Download PDFInfo
- Publication number
- CN1603309A CN1603309A CN200410041602.8A CN200410041602A CN1603309A CN 1603309 A CN1603309 A CN 1603309A CN 200410041602 A CN200410041602 A CN 200410041602A CN 1603309 A CN1603309 A CN 1603309A
- Authority
- CN
- China
- Prior art keywords
- tryptophane
- acetyl
- reaction
- glycolylurea
- methylene radical
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000010523 cascade reaction Methods 0.000 title claims abstract description 11
- DZTHIGRZJZPRDV-UHFFFAOYSA-N N-acetyltryptophan Chemical compound C1=CC=C2C(CC(NC(=O)C)C(O)=O)=CNC2=C1 DZTHIGRZJZPRDV-UHFFFAOYSA-N 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 150000002475 indoles Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 14
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 abstract 4
- UJIBFPBOBFXMKO-UHFFFAOYSA-N 5-methylideneimidazolidine-2,4-dione Chemical compound C=C1NC(=O)NC1=O UJIBFPBOBFXMKO-UHFFFAOYSA-N 0.000 abstract 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 abstract 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 abstract 2
- 230000021736 acetylation Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N tryptophan Chemical compound C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 11
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 6
- 229960004799 tryptophan Drugs 0.000 description 6
- ROILIXRRNBZNTC-UHFFFAOYSA-N CN(C(=O)N)C(CO)=O.N1C=CC2=CC=CC=C12 Chemical compound CN(C(=O)N)C(CO)=O.N1C=CC2=CC=CC=C12 ROILIXRRNBZNTC-UHFFFAOYSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 235000020776 essential amino acid Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 101710150975 N-acyl-L-amino acid amidohydrolase Proteins 0.000 description 1
- 239000006035 Tryptophane Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Indole Compounds (AREA)
Abstract
This invention relates a cascade reaction preparing method of chemical intermediate N-acetamide-DL-tryptophan. That is from indole methylene hydantoin, it is proceeded through hydrogenation, hydrolysis, acetylation three steps cascade reaction. The yield of N-acetamide-DL-tryptophan is about 80% comparing to indole methylene hydantoin. Acid and alkali dosages and equipment invest are reduced, and course consumption and product cost are reduced.
Description
Technical field
The present invention relates to the cascade reaction preparation method of chemical intermediate N-acetyl-DL-tryptophane, promptly begun by indoles methylene radical glycolylurea, through hydrogenation, hydrolysis, three step of acetylize cascade reaction, high yield obtains N-acetyl-DL-tryptophane.
Background technology
The L-tryptophane is one of indispensable amino acid required in human body and the animal life activity, and the growing of humans and animals, metabolism are played an important role, and is called as " second indispensable amino acid ", is widely used in aspects such as feed, medicine and food.As the 3rd limiting amino acid, in feed, add the nutritive value that the L-tryptophane will help improving feed, market demand should be more than ten thousand tons.Chemosynthesis-method for splitting both can chemosynthesis prepare DL-tryptophane (effect with feed grade L-tryptophane 60-70%), and also further enzymatic hydrolysis splits preparation L-tryptophane, has very strong universality.
It is L-Aminoacylase that present amino acid splits most widely used enzyme, and its substrate is acetylizad amino acid, is exactly N-acetyl-DL-tryptophane for tryptophane splits.Wherein, can provide raw material with low cost by indoles is initial for enzyme process splits preparation L-tryptophane via indoles methylene radical glycolylurea, indole methyl glycolylurea, the preparation of DL-tryptophane.
In general, forefathers adopt sodium hydroxide solution as the hydrogenation solvent in indoles methylene radical glycolylurea hydrogenation preparing indole methyl glycolylurea process, have hydrogenation effect preferably; And the basic hydrolysis of indole methyl glycolylurea is when preparing the DL-tryptophane, and one of its reactant also is a sodium hydroxide; When the acetylize of DL-tryptophane prepares N-acetyl-DL-tryptophane, generally also adopt sodium hydroxide solution as solvent.And three processes are independently carried out respectively, do not have association mutually.We are by independently the operating unit analysis is as can be known to three of indoles methylene radical glycolylurea hydrogenation, the hydrolysis of indole methyl glycolylurea, the acetylize of DL-tryptophane, there are some general character in these three reactions: reaction medium or reactant are sodium hydroxide solution, obtain product and all need to regulate the pH value after the reaction end, operation steps is loaded down with trivial details; Simultaneously, experiment shows that the side reaction product in each step is to not influence of next step reaction.Thought according to above-described general character and systematology; can be with hydrogenation, hydrolysis, be combined as a cascade reaction process three independent dispersive operating unit reactive systems of acetylize, regulate the loaded down with trivial details operation steps of pH value, loss and the facility investment in the reaction process repeatedly thereby reduce.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts hydrogenation-hydrolysis-acetylize cascade reaction to prepare N-acetyl-DL-tryptophane, this method improves product yield, reduces significant loss and consumption, reduces the pollution to environment.
Purpose of the present invention can reach by following measure:
A kind of cascade reaction prepares the method for N-acetyl-DL-tryptophane, it is characterized in that hydrogenation-hydrolysis-acetylation can be undertaken by following method: in autoclave, add the 0.5-1.0molL of reactor volume 40-60%
-1Sodium hydroxide solution, 100-400g indoles methylene radical glycolylurea is with respect to the Raney-Ni catalyzer 10%-30% of indoles methylene radical glycolylurea weight percent, at 3.0-4.0Mpa, 45-80 ℃ is reacted 1.5-4h down, after reaction finishes, after filtration, concentrate 4-6 doubly, in autoclave, 120-145 ℃ of following hydrolysis reaction 0.5-1.5h, after reaction finished, the ice-water bath cooling was stirred and is slowly dripped 6molL down
-1Hydrochloric acid regulate pH to 8.0-9.0, according to the doubly disposable adding diacetyl oxide of 1.2-1.4 of indoles methylene radical glycolylurea amount of substance, stir 0.5-1h after, regulate pH2.0 and can get white precipitate, filtration, drying can get N-acetyl-DL-tryptophane.
Beneficial effect of the present invention:
1, the present invention adopts hydrogenation-hydrolysis-acetylize cascade reaction to prepare the yield raising of N-acetyl-DL-tryptophane, is about 80% with respect to indoles methylene radical glycolylurea.
2, owing to adopt same solvent (or reactant), the consumption of the required sodium hydroxide of preparation 1t N-acetyl-tryptophane is reduced to 1.4t by 4.1t, also is reduced to 4.2t by 11.5t and regulate the required hydrochloric acid consumption of pH value repeatedly.
3, owing to will regulate the pH value repeatedly and change into and once regulate the pH value, the also corresponding minimizing of the minimizing of sepn process, facility investment.
Embodiment
Embodiment 1:
In the 10L autoclave, add Raney-Ni catalyzer 50g, 200g indoles methylene radical glycolylurea, 1.0molL
-1Sodium hydroxide solution 4L.At 3.0Mpa, 45 ℃ are reacted 4h down.After reaction finishes, after filtration, be concentrated into 1L.In autoclave, 145 ℃ of following hydrolysis reaction 1h.After reaction finished, the ice-water bath cooling was stirred and is slowly dripped 6molL down
-1Hydrochloric acid 400mL.Disposable adding diacetyl oxide 200mL behind the stirring 0.5h, regulates pH2.0 and can get white precipitate, filters, and drying can get N-acetyl-DL-tryptophane 173.4g, and its yield mean value is 80%.
Embodiment 2:
In the 10L autoclave, add Raney-Ni catalyzer 20g, 100g indoles methylene radical glycolylurea, 0.5molL
-1Sodium hydroxide solution 4L.At 3.0Mpa, 80 ℃ are reacted 1.5h down.After reaction finishes, after filtration, be concentrated into 1L.In autoclave, 125 ℃ of following hydrolysis reaction 1.5h.After reaction finished, the ice-water bath cooling was stirred and is slowly dripped 6molL down
-1Hydrochloric acid 200mL.Disposable adding diacetyl oxide 110mL behind the stirring 1h, regulates pH2.0 and can get white precipitate, filters, and drying can get N-acetyl-DL-tryptophane 89.5g, and its yield mean value is 82.3%.
Embodiment 3:
In the 10L autoclave, add Raney-Ni catalyzer 120g, 400g indoles methylene radical glycolylurea, 1.0molL
-1Sodium hydroxide solution 6L.At 4.0Mpa, 60 ℃ are reacted 2h down.After reaction finishes, after filtration, be concentrated into 1L.In autoclave, 145 ℃ of following hydrolysis reaction 1.5h.After reaction finished, the ice-water bath cooling was stirred and is slowly dripped 6molL down
-1Hydrochloric acid 600mL.Disposable adding diacetyl oxide 450mL behind the stirring 0.5h, regulates pH2.0 and can get white precipitate, filters, and drying can get N-acetyl-DL-tryptophane 340g, and its yield mean value is 78.6%.
Claims (1)
1. a cascade reaction prepares the method for N-acetyl-DL-tryptophane, it is characterized in that hydrogenation-hydrolysis-acetylation can be undertaken by following method: in autoclave, add the 0.5-1.0molL of reactor volume 40-60%
-1Sodium hydroxide solution, 100-400g indoles methylene radical glycolylurea is with respect to the Raney-Ni catalyzer 10%-30% of indoles methylene radical glycolylurea weight percent, at 3.0-4.0Mpa, 45-80 ℃ is reacted 1.5-4h down, after reaction finishes, after filtration, concentrate 4-6 doubly, in autoclave, 120-145 ℃ of following hydrolysis reaction 0.5-1.5h, after reaction finished, the ice-water bath cooling was stirred and is slowly dripped 6molL down
-1Hydrochloric acid regulate pH to 8.0-9.0, according to the doubly disposable adding diacetyl oxide of 1.2-1.4 of indoles methylene radical glycolylurea amount of substance, stir 0.5-1h after, regulate pH2.0 and can get white precipitate, filtration, drying can get N-acetyl-DL-tryptophane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041602.8A CN1256325C (en) | 2004-08-04 | 2004-08-04 | Process for cascade reaction preparation of N-acetyl-DL-tryptophan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041602.8A CN1256325C (en) | 2004-08-04 | 2004-08-04 | Process for cascade reaction preparation of N-acetyl-DL-tryptophan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1603309A true CN1603309A (en) | 2005-04-06 |
| CN1256325C CN1256325C (en) | 2006-05-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410041602.8A Expired - Fee Related CN1256325C (en) | 2004-08-04 | 2004-08-04 | Process for cascade reaction preparation of N-acetyl-DL-tryptophan |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1256325C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424073C (en) * | 2005-09-27 | 2008-10-08 | 上海化工研究院 | Synthesis of DL-tryptophane-alpha-N |
| CN114410344A (en) * | 2021-12-26 | 2022-04-29 | 中海油天津化工研究设计院有限公司 | Catalytic conversion method for inferior oil product |
-
2004
- 2004-08-04 CN CN200410041602.8A patent/CN1256325C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424073C (en) * | 2005-09-27 | 2008-10-08 | 上海化工研究院 | Synthesis of DL-tryptophane-alpha-N |
| CN114410344A (en) * | 2021-12-26 | 2022-04-29 | 中海油天津化工研究设计院有限公司 | Catalytic conversion method for inferior oil product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1256325C (en) | 2006-05-17 |
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| C14 | Grant of patent or utility model | ||
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Granted publication date: 20060517 Termination date: 20100804 |