CN105061289A - Preparation method of pharmaceutical grade L-tryptophan - Google Patents
Preparation method of pharmaceutical grade L-tryptophan Download PDFInfo
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- CN105061289A CN105061289A CN201510460051.7A CN201510460051A CN105061289A CN 105061289 A CN105061289 A CN 105061289A CN 201510460051 A CN201510460051 A CN 201510460051A CN 105061289 A CN105061289 A CN 105061289A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a preparation process of pharmaceutical grade L-tryptophan. The process includes dissolution, decolorization, pH adjustment, filtering and washing, drying and other steps. Specifically, the dissolution refers to dissolution of an L-tryptophan crude product in a solvent, and the solvent and the crude product are in a weight ratio of 100:50-60. The process provided by the invention is simple, and the refined L-tryptophan is in line with the standards of 2010 edition of Chinese pharmacopoeia. The process can realize mass refining production of L-tryptophan, and solves the disadvantages of excessive solvent consumption, low crystal concentration, and difficult realization of large-scale industrial production in the L-tryptophan refining process.
Description
Technical field
The present invention relates to one and prepare the amino acid whose preparation method of pharmaceutical grade, be specifically related to a kind of process for purification of L-Trp, be prepared into pharmaceutical grade L-Trp.
Background technology
Tryptophane chemistry tryptophane by name, is separated and obtains for 1902 from casein.Tryptophane has isomer in 3, is respectively L-type, D type and raceme DL type.Tryptophane is a kind of important nutritional necessary amino acid, can only have microorganism or phytosynthesis.L-Trp is wherein one of 8 seed amino acids of needed by human, and humans and animals cannot self synthesize, and can only absorb from food.There is metabolism hardly in D-trp, also nontoxicity in human body, and therefore human body does not need to supplement.L-Trp, as a kind of essential amino acid, is widely used in the aspect such as medicine, food and feeds at present.L-Trp structural formula is:
L-Trp medically has important application.In vivo, L-Trp metabolic conversion can produce the physiologically active substances such as serotonin, indolylacetic acid, nicotinic acid, melatonin, pigment, alkaloid, coenzyme, plant hormone, and tryptophan metabolism imbalance can cause diabetes or mentally deranged.L-Trp has medically been widely used in the treatment for the treatment of pellagra, treatment of schizophrenia, nutrient amino acids sheet etc.Therefore the demand of pharmaceutical grade L-Trp just grows with each passing day.
L-Trp belongs to heat-sensitive substance, long-time heating or illumination easy coloring, easily decomposes rotten, so commonly use proteolysis method, chemical synthesis, enzyme law catalysis or directly carry out fermentative production L-Trp in Study on extraction.Usually the L-Trp that these methods are obtained is due to color dark (being often lark), and containing other amino acid impurity of part and other water-soluble proteins etc., transmittance, content and specific optical rotation are difficult to reach standards of pharmacopoeia, only can reach feed grade amino acid standard.Some bibliographical informations process for purification of L-Trp, but there is distinct disadvantage, or treating process uses solvent too much, cannot large-scale production, or refining after L-Trp cannot reach standards of pharmacopoeia.
The process for purification of L-Trp, relevant report is as follows:
CN200810019958.X (publication number is CN101531626A) discloses the process for purification of industrialized production of L-tryptophan by biofermentation method, comprise the following steps: under agitation crude product is added in 60 DEG C of pure water of 20 times of weight, be warming up to 75 DEG C of dissolvings, add alum by crude product weight 0.1%; Add 303# gac by 30% of crude product weight, 75 DEG C decolour 15 minutes; Destainer is cooled to 5-15 DEG C, and 15% adds concentration 80% industrial acetic acid by volume, stirs insulation 5 ± 3 DEG C of crystallizations 4 hours; Crystal solution whizzer is separated, frozen water drip washing, within 80 DEG C vacuum-drying 4-6 hour, obtains fine work.The maximum shortcoming of present method uses solvent amount too large.Because the solubleness of L-Trp in pure water is very little, therefore use the water of 20 times of weight at high temperature to make L-Trp clearly molten, namely the refining concentration of L-Trp is less than 5%, and this technology has highlighted the shortcoming that L-Trp highly finished product are difficult to produce in enormous quantities.
CN201010560069.1 (publication number is CN102030698A) discloses the method utilizing organic membrane separation and Extraction fermentation L-Trp, first by the pH regulator of fermented liquid to certain value, then carry out micro-filtration-ultrafiltration system batch can and carry out membrane filtration, adjust ph again, concentrated, alcohol crystallization, to obtain final product.This invention provides the method from broth extraction L-Trp crude product, do not provide the process for purification of L-Trp, the L-Trp of preparation is difficult to the quality standard reaching pharmaceutical grade L-Trp.
CN200910065010.2 (publication number is CN101565396A) discloses a kind of process for refining of L-Trp.Concrete grammar is with water and propanol solvent mixture for solvent, and by L-Trp dissolving crude product, react 100-120min after dissolving at 50-80 DEG C, the clear liquor crystallization after filtration obtains L-Trp highly finished product.With mass ratio range, wherein the consumption of solvent is solvent: crude product=100:20-30.Obtained L-Trp transmittance >=90%, specific rotation is-30.0-32.5 degree, yield about 85%.In this invention, solvent employs the mixed solvent of water and alcohol, add the solubleness of L-Trp, but solvent usage quantity is still larger, solvent usage quantity is 4-5 times of L-Trp crude product weight, and product transmittance be difficult to reach standards of pharmacopoeia regulation >=95.0%, also illustrate that the decolorizing effect of L-Trp in the mixed solvent of alcohol and water is not ideal.This technological invention can not stably produce pharmaceutical grade L-Trp.
So far, also there is not pertinent literature report to use the solvent of less amount to refine L-Trp to solve further, and reach the technological invention of pharmaceutical grade standard.
Summary of the invention
The object of this invention is to provide a kind of effective process for purification, feed grade L-Trp is refined into pharmaceutical grade L-Trp.Consume solvent in solution L-Trp treating process excessive, crystallisation concentration is lower, cannot realize the shortcoming that large-scale industrialization is produced simultaneously.
A kind of method preparing pharmaceutical grade L-Trp provided by the invention, the method comprises the following steps:
1) dissolve: by feed grade L-Trp dissolving crude product in solvent, with mass ratio range, solvent: crude product is 100:50-60;
2) decolour: the molten clear liquid of above-mentioned L-Trp is added activated carbon decolorizing, filter, obtain achromaticity and clarification filtrate;
3) pH is regulated: the filtrate after decolouring is regulated pH to 5.4-6.4, obtains L-Trp crystal;
4) washing is filtered: after the centrifugation of L-Trp crystal, damp product wash with water again, and centrifugation goes out crystal;
5) dry: by L-Trp crystal vacuum drying, to obtain final product.
In above-mentioned process for purification:
Step 1) in:
In described feed grade L-Trp, the content of L-Trp should be not less than 95%.
Described solvent is aqueous sodium carbonate or aqueous sodium hydroxide solution, and its concentration is the aqueous sodium hydroxide solution of 5-8%, preferred 5%-8%;
Solvent temperature controls at 50-60 DEG C;
Step 2) in:
The consumption of gac is 5% of L-Trp crude product weight;
Bleaching time is 0.5-1h;
Step 3) in:
Filtrate adjust pH temperature controls at 40-50 DEG C;
PH adjusting agent to be concentration be 10% hydrochloric acid;
Step 4) in:
During centrifugation, rotating speed is 1500-2000rpm, and the time is 15-30min, and preferably, rotating speed is 1700rpm, and the time is 20min;
Step 5) in:
Vacuum-drying temperature and time is respectively 50-70 DEG C, 10h, and vacuum tightness is-0.09MPa--0.1MPa.
Preferably, said method comprising the steps of:
1) dissolve:
By feed grade L-Trp dissolving crude product in solvent, wherein solvent is sodium carbonate or the aqueous sodium hydroxide solution of 5%-8%, and solvent temperature is 50-60 DEG C, with mass ratio range, and solvent: crude product is 10:5-6;
2) decolour:
By adding the activated carbon decolorizing 0.5h of L-Trp crude product weight 5% under the molten clear liquid insulation of above-mentioned L-Trp, after filtered while hot, obtain achromaticity and clarification filtrate;
3) pH is regulated:
By at filtrate 40-50 DEG C after decolouring, then regulate pH=5.4-6.4 with hydrochloric acid, obtain L-Trp crystal;
4) washing is filtered:
Solution centrifugal containing L-Trp crystal is separated, obtain L-Trp tide product, then after washing 2 times with water, centrifugation goes out crystal;
5) dry:
At 50-70 DEG C, L-Trp crystal after vacuum drying 10h, vacuum tightness is-0.09MPa ~-0.1MPa, the airtight preservation of vacuum packaging.
Process for purification provided by the invention has the following advantages:
1, use solvent few, the solvent that the present invention uses is compared to patent CN101565396A and CN101531626A, and solvent consumption significantly reduces, and identical equipment can produce more pharmaceutical grade L-Trp.Because solvent consumption is few, decrease the energy consumption that heat-processed consumes, provide cost savings.
2, method disclosed in patent CN101565396A, its mixed solvent used cannot recycling, and the present invention can co-producing sodium chloride byproduct.
3, the present invention can effectively remove the impurity such as other protein through alkali tune and heating steps and increase the solubleness of L-Trp in water, effectively transmittance can be improved by bleaching process, high yield can be realized by reducing solvent consumption, utilizing vacuum packaging can effectively avoid L-Trp oxidized in atmosphere.Therefore the present invention high yield can prepare pharmaceutical grade L-Trp.
4, the technical solution used in the present invention is dissolved in alkaline aqueous solution by feed grade L-Trp very little for solubleness in water, the sodium salt of the L-Trp that production solubleness is larger.Decoloured by Medicinal Charcoal again, remove pigment and other protein impurities, after filtration, obtain the L-Trp sodium-salt aqueous solution clarified.Then use salt acid for adjusting pH value to the iso-electric point of L-Trp, the L-Trp of insoluble and crystallize out.Centrifugation, then the salt that washing removing is remaining, centrifugation post-drying is packed.
5, process for purification provided by the invention, its yield is more than or equal to 90%, specific optical rotation-30.0-32.5 degree, and transmittance >=95.0%, content >=99.0%, product index meets standards of pharmacopoeia.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
In following examples, feed grade L-Trp is that Anhui Fengyuan Fermentation Technology Engineering Research Co., Ltd. produces, content >=95.0%.
Embodiment 1
1) dissolve: get feed grade L-Trp crude product 50kg and put in 200L enamel still, add the aqueous sodium hydroxide solution 100kg (solvent: the weight ratio of crude product is 10:5) of 5%, stir, be heated to 60 DEG C of insulated and stirred, L-Trp is all dissolved.
2) decolour: molten clear after add gac 2.5kg (being equivalent to 5% of feed grade L-Trp crude product weight), at 60 DEG C, insulation decolouring 0.5h, is filtered in 200L crystallization enamel still through 0.22 μm of titanium rod while hot, obtains achromaticity and clarification filtrate.
3) regulate pH: the filtrate after decolouring is cooled to 50 DEG C, then regulate the pH6.0 of filtrate with the hydrochloric acid that concentration is 10%, produce a large amount of L-Trp white crystal.
4) washing is filtered: by step 3) obtain crystal whipped state borehole cooling to room temperature, centrifugation 20min (centrifuge speed 1700rpm), obtain L-Trp tide product white crystal, use purified water 10kg, wash 2 times, centrifugation 20min (centrifuge speed 1700rpm), obtains L-Trp highly finished product.
5) dry: at 60 DEG C after vacuum drying 10h, the airtight preservation of vacuum packaging.
Embodiment 2
1) dissolve: get feed grade L-Trp crude product 60kg and put in 200L enamel still, add the aqueous sodium hydroxide solution 100kg (solvent: the weight ratio of crude product is 10:6) of 5%, stir, be heated to 50 DEG C of insulated and stirred, L-Trp is all dissolved.
2) decolour: molten clear after add gac 3kg (being equivalent to 5% of feed grade L-Trp crude product), at 50 DEG C, insulation decolouring 0.5h, is filtered in 200L crystallization enamel still through 0.22 μm of titanium rod while hot, obtains achromaticity and clarification filtrate.
3) regulate pH: the filtrate after decolouring is cooled to 45 DEG C, then regulate the pH of filtrate to be 6.4 with the hydrochloric acid of 10%, produce a large amount of L-Trp white crystal.
4) washing is filtered: by step 3) obtain crystal whipped state borehole cooling to room temperature, centrifugation 20min (centrifuge speed 1700rpm), obtain L-Trp tide product white crystal, use purified water 12kg, wash 2 times, centrifugation 20min (centrifuge speed 1700rpm), obtains L-Trp highly finished product.
5) dry: at 50 DEG C after vacuum drying 10h, the airtight preservation of vacuum packaging.
Embodiment 3
1) dissolve: get feed grade L-Trp crude product 60kg and put in 200L-enamel still, add the aqueous sodium hydroxide solution 100kg (solvent: the weight ratio of crude product is 10:6) of 8%, stir, be heated to 55 DEG C of insulated and stirred, L-Trp is all dissolved.
2) decolour: molten clear after add gac 3kg (being equivalent to 5% of feed grade L-Trp crude product weight), at 55 DEG C, insulation decolouring 0.5h, is filtered in 200L crystallization enamel still through 0.22 μm of titanium rod while hot, obtains achromaticity and clarification filtrate.
3) regulate pH: the filtrate after decolouring is cooled to 40 DEG C, then regulate the pH5.4 of filtrate with the hydrochloric acid that concentration is 10%, produce a large amount of L-Trp white crystal.
4) washing is filtered: by step 3) obtain crystal whipped state borehole cooling to room temperature, centrifugation 20min (centrifuge speed 1700rpm), obtain L-Trp tide product white crystal, use purified water 12kg, wash 2 times, centrifugation 20min (centrifuge speed 1700rpm), obtains L-Trp highly finished product.
5) dry: at 70 DEG C after vacuum drying 10h, the airtight preservation of vacuum packaging.
Comparative example 1
Process for refining disclosed in CN101565396A is adopted to refine.
Experimental example 1: the comparison on yield, product index
Compare the method for embodiment 1-3 and comparative example 1, concrete outcome is in table 1:
Refining of table 1:L-tryptophane
Table 1 result shows: the yield of embodiment 1-3 is not less than 91%, and purity is not less than 99%, and its transparence of the product of preparation and specific optical rotation are also better than comparative example 1.Result shows: the process for purification of L-Trp of the present invention, and product yield is high, and solvent consumption is few, and product index can reach pharmaceutical grade standard.
Although above with general explanation, embodiment and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. prepare a method for pharmaceutical grade L-Trp, it is characterized in that, comprise the following steps:
1) dissolve: by feed grade L-Trp dissolving crude product in solvent, with mass ratio range, solvent: crude product is 100:50-60;
2) decolour: the molten clear liquid of above-mentioned L-Trp is added activated carbon decolorizing, filter, obtain achromaticity and clarification filtrate;
3) pH is regulated: the filtrate after decolouring is regulated pH to 5.4-6.4, obtains L-Trp crystal;
4) washing is filtered: after the centrifugation of L-Trp crystal, damp product wash with water again, and centrifugation goes out crystal;
5) dry: by L-Trp crystal vacuum drying, to obtain final product.
2. method according to claim 1, is characterized in that, in described feed grade L-Trp, the content of L-Trp should be not less than 95%.
3. method according to claim 1, is characterized in that, described step 1) in solvent be aqueous sodium carbonate or aqueous sodium hydroxide solution, preferred concentration is 5-8%.
4. method according to claim 1, is characterized in that, described step 1) dissolve time temperature control at 50-60 DEG C.
5. method according to claim 1, is characterized in that, described step 2) consumption of gac is 5% of L-Trp crude product weight.
6. method according to claim 1, is characterized in that, described step 2) time of activated carbon decolorizing is 0.5-1h.
7. method according to claim 1, is characterized in that, described step 4) centrifugation time, rotating speed is 1500-2000rpm, and the time is 15-30min.
8. method according to claim 1, is characterized in that, described step 3) in pH adjusting agent to be concentration be 10% hydrochloric acid.
9. method according to claim 1, is characterized in that, described step 3) in filtrate adjust pH temperature control at 40-50 DEG C.
10. the method according to any one of claim 1-9, is characterized in that, said method comprising the steps of:
1) dissolve:
By feed grade L-Trp dissolving crude product in solvent, wherein solvent is sodium carbonate or the aqueous sodium hydroxide solution of 5%-8%, and solvent temperature is 50-60 DEG C, with mass ratio range, and solvent: crude product is 10:5-6;
2) decolour:
By adding the activated carbon decolorizing 0.5h of feed grade L-Trp crude product weight 5% under the molten clear liquid insulation of above-mentioned L-Trp, after filtered while hot, obtain achromaticity and clarification filtrate;
3) pH is regulated:
Regulate pH to be 5.4-6.4 by filtrate 40-50 DEG C after decolouring, obtain L-Trp crystal;
4) washing is filtered:
Solution containing L-Trp crystal is down to room temperature, then centrifugation, obtain L-Trp tide product, then after washing 2 times with water, recentrifuge, isolates crystal;
5) dry:
At 50-70 DEG C, L-Trp crystal after vacuum drying 10h, vacuum tightness is-0.09MPa ~-0.1MPa, the airtight preservation of vacuum packaging.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481750A (en) * | 2015-12-10 | 2016-04-13 | 河南巨龙生物工程股份有限公司 | Method used for extracting high-purity pharmaceutical-grade tryptophan |
| CN111410627A (en) * | 2020-04-03 | 2020-07-14 | 石家庄市冀荣药业有限公司 | production method of pharmaceutical-grade L-tryptophan |
| CN113354569A (en) * | 2021-06-04 | 2021-09-07 | 无锡晶海氨基酸股份有限公司 | Method for purifying tryptophan |
| CN116283711A (en) * | 2023-02-21 | 2023-06-23 | 黑龙江新和成生物科技有限公司 | Preparation method of high-purity cake-shaped L-tryptophan crystal and product thereof |
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| CN101531626A (en) * | 2008-03-14 | 2009-09-16 | 江苏诚意药业有限公司 | Refining method for producing L-tryptophan in industrial way by using biofermentation method |
| CN101550101A (en) * | 2009-01-20 | 2009-10-07 | 福建省建阳武夷味精有限公司 | Method for clean purifying L-tryptophan by utilizing fermented liquid |
| CN102146052A (en) * | 2010-12-24 | 2011-08-10 | 山东鲁抗医药股份有限公司 | Method for preparing tryptophan |
| CN102304077A (en) * | 2011-06-24 | 2012-01-04 | 南通诚信氨基酸有限公司 | Method for purifying tryptophan |
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2015
- 2015-07-28 CN CN201510460051.7A patent/CN105061289B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101531626A (en) * | 2008-03-14 | 2009-09-16 | 江苏诚意药业有限公司 | Refining method for producing L-tryptophan in industrial way by using biofermentation method |
| CN101550101A (en) * | 2009-01-20 | 2009-10-07 | 福建省建阳武夷味精有限公司 | Method for clean purifying L-tryptophan by utilizing fermented liquid |
| CN102146052A (en) * | 2010-12-24 | 2011-08-10 | 山东鲁抗医药股份有限公司 | Method for preparing tryptophan |
| CN102304077A (en) * | 2011-06-24 | 2012-01-04 | 南通诚信氨基酸有限公司 | Method for purifying tryptophan |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481750A (en) * | 2015-12-10 | 2016-04-13 | 河南巨龙生物工程股份有限公司 | Method used for extracting high-purity pharmaceutical-grade tryptophan |
| CN105481750B (en) * | 2015-12-10 | 2018-02-27 | 河南巨龙生物工程股份有限公司 | A kind of process for extracting high-purity medicine rank tryptophan |
| CN111410627A (en) * | 2020-04-03 | 2020-07-14 | 石家庄市冀荣药业有限公司 | production method of pharmaceutical-grade L-tryptophan |
| CN113354569A (en) * | 2021-06-04 | 2021-09-07 | 无锡晶海氨基酸股份有限公司 | Method for purifying tryptophan |
| CN116283711A (en) * | 2023-02-21 | 2023-06-23 | 黑龙江新和成生物科技有限公司 | Preparation method of high-purity cake-shaped L-tryptophan crystal and product thereof |
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