CN102827018A - Preparation method of N-acetyl-L-tyrosine - Google Patents
Preparation method of N-acetyl-L-tyrosine Download PDFInfo
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- CN102827018A CN102827018A CN2012103576748A CN201210357674A CN102827018A CN 102827018 A CN102827018 A CN 102827018A CN 2012103576748 A CN2012103576748 A CN 2012103576748A CN 201210357674 A CN201210357674 A CN 201210357674A CN 102827018 A CN102827018 A CN 102827018A
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Abstract
The invention discloses a preparation method of N-acetyl-L-tyrosine and belongs to the field of preparation of amino acid. The preparation method comprises the steps of: mixing L-tyrosine as a main raw material with acetic anhydride, caustic soda liquid, hydrochloric acid, pure water and activated carbon as auxiliary materials; acetylizing, neutralizing, crystallizing, refining and the like on the L-tyrosine to prepare an N-acetyl-L-tyrosine quality product. Equipment used in the preparation method comprise a chemical reaction kettle, a crystallization kettle, a precision filter, a centrifugal machine, a concentracting tank, a refining neutralization kettle and a dryer which are universal. The preparation method has the advantages that the preparation efficiency is high, the process is simple, the raw material price is low, polluted wastes can not be discharged, the product quality is high and the like, and the N-acetyl-L-tyrosine is mainly used as a fine organic chemical intermediate.
Description
Technical field:
The invention belongs to the amino acid production field, relate in particular to the method for a kind of N-of production acetyl-L-tyrosine.
Background technology:
N-acetyl-L-tyrosine has another name called NSC 10853, and outward appearance is white crystals or crystalline powder; Tart flavour is arranged, and molecular formula is C11H13NO4, and molecular weight is 223.23; 47.5 ° of specific rotatory powers; Fusing point is 149 ℃-152 ℃, and N-acetyl-L-tyrosine is important meticulous organic chemical industry's midbody, is widely used in fields such as medicine, agricultural chemicals, chemical industry.Though the production technique of this product is a lot, the most directly production technique is exactly with the acetylize of L-tyrosine, and L-tyrosine is a kind of aromatic series polarity alpha amino acid that contains phenolic hydroxyl group, is a kind of in 20 seed amino acids of constitutive protein matter; Be mammiferous indispensable amino acid, outward appearance is white crystals body or crystalline powder, and is tasteless; Be soluble in formic acid, be insoluble in water, be insoluble to ethanol and ether; Molecular formula is C9H11NO3, and molecular weight is 181.20, and specific rotatory power L-body is-10.6 °.The main application of L-tyrosine is: 1. the catalytic substrate that is tyrosine oxidase list phenolase function; It is the final main raw material that forms excellent melanocyte and pheomelanin; In the skin-lightening cosmetic research and development; Can be through studying the generation that synthetic tyrosine oxidase analog with the tyrosine competition can suppress melanocyte effectively, patients with vitiligo is eaten the food that contains tyrosine can promote melanic formation, alleviates the vitiligo symptom; 2. foodstuff additive; 3. being a kind of important biochemical reagents, is the main raw material of medicines such as synthetic peptide hormone, microbiotic, L-DOPA; 4. be widely used in research of agricultural science, also make drink additive and the artificial insect feedstuff of preparation.Product of the present invention is to be raw material with tyrosine; Through the acetylize of tyrosine being produced N-acetyl-L-tyrosine; So-called acetylize is exactly with the reaction of introducing ethanoyl CH3CO-on the nitrogen in the organic compound molecule, oxygen, the carbon atom, is meant in amino acid ethanoyl is transferred to the process on the amino acid side chain group that acetylizing agent commonly used has Acetyl Chloride 98Min., aceticanhydride and Glacial acetic acid min. 99.5 etc.; Wherein cheap and easy to get with Glacial acetic acid min. 99.5, excess acetyl chloride is the fastest.Also can carry out acetylization reaction in the organism, form like the choline acetylize and generate vagusstoff, the acetylize of grape amine generates acetyl grape amine; And for example synthetic, the terpenoid of lipid acid, Serlabo, steroid is synthetic, all must be through a series of acetylization reaction.The present invention is a main raw material with L-tyrosine; With aceticanhydride, liquid caustic soda, hydrochloric acid, pure water, gac is auxiliary material; Operations such as the mixing through supplementary material, the acetylize of L-tyrosine, neutralization, crystallization, refining, oven dry, pulverizing; Make N-acetyl-L-tyrosine elaboration; The equipment that this technology is used has: chemical reaction kettle, crystallization kettle, accurate filter, whizzer, concentration tank, refining in and still, dryer, the equipment of use is general-purpose equipment, has the production efficiency height, series of advantages such as technology is simple, cost of material is low, pollution-free waste discharge, quality product height.
Summary of the invention
The problem that the present invention mainly solves provides the working method of a kind of N-acetyl-L-tyrosine; This method is a main raw material with L-tyrosine; With aceticanhydride, liquid caustic soda, hydrochloric acid, pure water, gac is auxiliary material; Operations such as the mixing through supplementary material, the acetylize of L-tyrosine, neutralization, crystallization, refining, oven dry, pulverizing; Make finished product; The weight proportion of the raw material that the present invention uses is: refining L-tyrosine pulvis 14%-16%, aceticanhydride 19%-21%, concentration are that 20% liquid caustic soda 25%, pure water 40%, concentration are that 30% hydrochloric acid is an amount of, gac is an amount of, the equipment that uses as chemical reaction kettle, crystallization kettle, accurate filter, whizzer, concentration tank, refining in and still, dryer, kibbler.
The present invention can realize through following technical scheme:
The working method of a kind of N-acetyl-L-tyrosine is characterized in that being made up of following steps:
(1) is that 20% liquid caustic soda solution is sent into reaction kettle with the concentration of formula ratio, adds pure water, the elaboration L-tyrosine of formula ratio again, the reaction kettle sealing is evacuated to vacuum; Aceticanhydride at vacuum condition decline formula ratio is sent into reaction kettle, while stirring steam is sent into the reaction kettle interlayer and heats up, and makes under the condition of sealing that mixing liquid is little in the still to boil; Keep temperature-resistant, used stirrer slow stirring reaction 1.9-2.1 hour, make the acetylize of L-tyrosine; In the reaction reaction solution chemical examination that the later stage can take a morsel; Do not contain under the situation of tyrosine in affirmation, stop to stir and heating, finish reaction; Obtain filtrating after using natural filtration frame elimination impurity then, filtrating is squeezed into crystallization kettle via pump.
(2) be after 30% hydrochloric acid filters through accurate filter with concentration; Filtrating in the crystallization kettle neutralizes; Add hydrochloric acid while stirring and measure the pH value simultaneously, when pH reaches 4.4-4.6, stop to add hydrochloric acid, the circulation cool brine that at this moment freon refrigerator is produced is sent into the cooling of crystallization kettle interlayer; The filtrating temperature remains on 0 ℃-3 ℃ in the control still; Under this temperature, slowly stir crystallization in 12 hours, after crystallization finishes all materials are sent into whizzer elimination filtrating, obtain first N-acetyl-L-tyrosine bullion; Obtain filtrating and return concentration tank, sent into the crystallization kettle crystallisation by cooling once more 12 hours after being concentrated into half of volume, obtain second batch of N-acetyl-L-tyrosine bullion, first is merged with second batch of bullion use.
(3) N-acetyl-L-tyrosine bullion is sent into reaction kettle, add rising temperature for dissolving behind an amount of pure water, add gac when being heated to 70 ℃; Constant temperature stirs decolouring 0.5 hour, obtains clear liquid after using 0.5 square metre of half frame to filter then, with the clear liquid that obtains squeeze into refining in and still; The stillness of night, when being cooled to 0-3 ℃, constant temperature kept crystallization in 12 hours through in refining, feeding the circulation refrigerated brine with the still interlayer behind the naturally cooling; Crystallisate after the crystallization is sent into whizzer and is filtered; Promptly obtain the wet article of N-acetyl-L-tyrosine, the article of wetting are sent into negative pressure oven dry in the dryer, bake out temperature is 50 ℃-56 ℃; Drying time is 4-5 hour, and the caking thing pulverizing back dress after will drying then wraps into the storehouse and gets product.
(4) method of use of N-acetyl-L-tyrosine is: use as meticulous organic chemical industry's midbody.
The acetylizad reaction times of L-tyrosine is 2 hours in the step (1).
The drying temperature and the time of drying of drying machine correspond in the step (3): when bake out temperature was 50 ℃, drying time was 5 hours; When bake out temperature was 53 ℃, drying time was 4.5 hours; When bake out temperature was 56 ℃, drying time was 4 hours.
The invention has the beneficial effects as follows: the method that a kind of N-of batch process in batches acetyl-L-tyrosine is provided; This working method have use general-purpose equipment, technology is simple, raw material sources are abundant, reaction process is gentle, be easy to production operation, three-waste free discharge, series of advantages such as production cost is low and productive rate is high, good product quality, can mass-produce high-quality N-acetyl-L-tyrosine.
Embodiment
Embodiment below in conjunction with concrete describes in further detail the present invention.
Embodiment 1
With accounting for total amount is that 25% concentration is that 20% liquid caustic soda solution is sent into reaction kettle, and adding that to account for total amount be 40% pure water again, accounting for total amount is 14% elaboration L-tyrosine, and the reaction kettle sealing is evacuated to vacuum; Descending at vacuum condition, to account for total amount be that 21% aceticanhydride is sent into reaction kettle, while stirring steam sent into the reaction kettle interlayer and heat up, and makes under the condition of sealing that mixing liquid is little in the still to boil; Keep temperature-resistant; Used stirrer slow stirring reaction 1.9-2.1 hour, and made the acetylize of L-tyrosine, in the reaction solution chemical examination that can take a morsel of reaction later stage; Do not contain under the situation of tyrosine in affirmation; Stop to stir and heat and finish reaction, obtain filtrating after using natural filtration frame elimination impurity then, filtrating is squeezed into crystallization kettle via electric pump.With an amount of concentration is after 30% hydrochloric acid filters through accurate filter; Filtrating in the crystallization kettle neutralizes; Add hydrochloric acid while stirring and measure the pH value simultaneously, when pH reaches 4.4-4.6, stop to add hydrochloric acid, the circulation cool brine that at this moment freon refrigerator is produced is sent into the cooling of crystallization kettle interlayer; The filtrating temperature remains on 0 ℃-3 ℃ in the control still; Under this temperature, slowly stir crystallization in 12 hours, after crystallization finishes all materials are sent into whizzer elimination filtrating, obtain first N-acetyl-L-tyrosine bullion; Obtain filtrating and return concentration tank, sent into the crystallization kettle crystallisation by cooling once more 12 hours after being concentrated into half of volume, obtain second batch of N-acetyl-L-tyrosine bullion, first is merged with second batch of bullion use.N-acetyl-L-tyrosine bullion is sent into reaction kettle, add rising temperature for dissolving behind an amount of pure water, add gac when being heated to 70 ℃; Constant temperature stirs decolouring 0.5 hour, obtains clear liquid after using 0.5 square metre of half frame to filter then, with the clear liquid that obtains squeeze into refining in and still; The stillness of night, when being cooled to 0-3 ℃, constant temperature kept crystallization in 12 hours through in refining, feeding the circulation refrigerated brine with the still interlayer behind the naturally cooling; Crystallisate after the crystallization is sent into whizzer and is filtered; Promptly obtain the wet article of N-acetyl-L-tyrosine, the article of wetting are sent into negative pressure oven dry in the dryer, bake out temperature is 50 ℃; Drying time is 5 hours, and the caking thing pulverizing back dress after will drying then wraps into the storehouse and gets product.The method of use of N-acetyl-L-tyrosine is: use as meticulous organic chemical industry's midbody.
Embodiment 2
With accounting for total amount is that 25% concentration is that 20% liquid caustic soda solution is sent into reaction kettle, and adding that to account for total amount be 40% pure water again, accounting for total amount is 15% elaboration L-tyrosine, and the reaction kettle sealing is evacuated to vacuum; Descending at vacuum condition, to account for total amount be that 20% aceticanhydride is sent into reaction kettle, while stirring steam sent into the reaction kettle interlayer and heat up, and makes under the condition of sealing that mixing liquid is little in the still to boil; Keep temperature-resistant; Used stirrer slow stirring reaction 1.9-2.1 hour, and made the acetylize of L-tyrosine, in the reaction solution chemical examination that can take a morsel of reaction later stage; Do not contain under the situation of tyrosine in affirmation; Stop to stir and heat and finish reaction, obtain filtrating after using natural filtration frame elimination impurity then, filtrating is squeezed into crystallization kettle via electric pump.With an amount of concentration is after 30% hydrochloric acid filters through accurate filter; Filtrating in the crystallization kettle neutralizes; Add hydrochloric acid while stirring and measure the pH value simultaneously, when pH reaches 4.4-4.6, stop to add hydrochloric acid, the circulation cool brine that at this moment freon refrigerator is produced is sent into the cooling of crystallization kettle interlayer; The filtrating temperature remains on 0 ℃-3 ℃ in the control still; Under this temperature, slowly stir crystallization in 12 hours, after crystallization finishes all materials are sent into whizzer elimination filtrating, obtain first N-acetyl-L-tyrosine bullion; Obtain filtrating and return concentration tank, sent into the crystallization kettle crystallisation by cooling once more 12 hours after being concentrated into half of volume, obtain second batch of N-acetyl-L-tyrosine bullion, first is merged with second batch of bullion use.N-acetyl-L-tyrosine bullion is sent into reaction kettle, add rising temperature for dissolving behind an amount of pure water, add gac when being heated to 70 ℃; Constant temperature stirs decolouring 0.5 hour, obtains clear liquid after using 0.5 square metre of half frame to filter then, with the clear liquid that obtains squeeze into refining in and still; The stillness of night, when being cooled to 0-3 ℃, constant temperature kept crystallization in 12 hours through in refining, feeding the circulation refrigerated brine with the still interlayer behind the naturally cooling; Crystallisate after the crystallization is sent into whizzer and is filtered; Promptly obtain the wet article of N-acetyl-L-tyrosine, the article of wetting are sent into negative pressure oven dry in the dryer, bake out temperature is 53 ℃; Drying time is 4.5 hours, and the caking thing pulverizing back dress after will drying then wraps into the storehouse and gets product.The method of use of N-acetyl-L-tyrosine is: use as meticulous organic chemical industry's midbody.
Embodiment 3
With accounting for total amount is that 25% concentration is that 20% liquid caustic soda solution is sent into reaction kettle, and adding that to account for total amount be 40% pure water again, accounting for total amount is 16% elaboration L-tyrosine, and the reaction kettle sealing is evacuated to vacuum; Descending at vacuum condition, to account for total amount be that 19% aceticanhydride is sent into reaction kettle, while stirring steam sent into the reaction kettle interlayer and heat up, and makes under the condition of sealing that mixing liquid is little in the still to boil; Keep temperature-resistant; Used stirrer slow stirring reaction 1.9-2.1 hour, and made the acetylize of L-tyrosine, in the reaction solution chemical examination that can take a morsel of reaction later stage; Do not contain under the situation of tyrosine in affirmation; Stop to stir and heat and finish reaction, obtain filtrating after using natural filtration frame elimination impurity then, filtrating is squeezed into crystallization kettle via electric pump.With an amount of concentration is after 30% hydrochloric acid filters through accurate filter; Filtrating in the crystallization kettle neutralizes; Add hydrochloric acid while stirring and measure the pH value simultaneously, when pH reaches 4.4-4.6, stop to add hydrochloric acid, the circulation cool brine that at this moment freon refrigerator is produced is sent into the cooling of crystallization kettle interlayer; The filtrating temperature remains on 0 ℃-3 ℃ in the control still; Under this temperature, slowly stir crystallization in 12 hours, after crystallization finishes all materials are sent into whizzer elimination filtrating, obtain first N-acetyl-L-tyrosine bullion; Obtain filtrating and return concentration tank, sent into the crystallization kettle crystallisation by cooling once more 12 hours after being concentrated into half of volume, obtain second batch of N-acetyl-L-tyrosine bullion, first is merged with second batch of bullion use.N-acetyl-L-tyrosine bullion is sent into reaction kettle, add rising temperature for dissolving behind an amount of pure water, add gac when being heated to 70 ℃; Constant temperature stirs decolouring 0.5 hour, obtains clear liquid after using 0.5 square metre of half frame to filter then, with the clear liquid that obtains squeeze into refining in and still; The stillness of night, when being cooled to 0-3 ℃, constant temperature kept crystallization in 12 hours through in refining, feeding the circulation refrigerated brine with the still interlayer behind the naturally cooling; Crystallisate after the crystallization is sent into whizzer and is filtered; Promptly obtain the wet article of N-acetyl-L-tyrosine, the article of wetting are sent into negative pressure oven dry in the dryer, bake out temperature is 56 ℃; Drying time is 4 hours, and the caking thing pulverizing back dress after will drying then wraps into the storehouse and gets product.The method of use of N-acetyl-L-tyrosine is: use as meticulous organic chemical industry's midbody.
Claims (4)
1. the working method of N-acetyl-L-tyrosine, the raw material weight proportioning of use is: refining L-tyrosine pulvis 14%-16%, aceticanhydride 19%-21%, concentration are that 20% liquid caustic soda 25%, pure water 40%, concentration are that 30% hydrochloric acid is an amount of, gac is an amount of, it is characterized in that: step (1) is that 20% liquid caustic soda solution is sent into reaction kettle with the concentration of formula ratio; The pure water, the elaboration L-tyrosine that add formula ratio again are evacuated to vacuum with the reaction kettle sealing, send into reaction kettle at the aceticanhydride of vacuum condition decline formula ratio; While stirring steam being sent into the reaction kettle interlayer heats up; Making under the condition of sealing that mixing liquid is little in the still boils, and keeps temperature-resistant, use stirrer slow stirring reaction 1.9-2.1 hour; Make the acetylize of L-tyrosine; In the reaction reaction solution chemical examination that the later stage can take a morsel, do not contain under the situation of tyrosine confirming, stop to stir and heat and finish reaction; Obtain filtrating after using natural filtration frame elimination impurity then, filtrating is squeezed into crystallization kettle via electric pump; Step (2) is after 30% hydrochloric acid filters through accurate filter with concentration; Filtrating in the crystallization kettle neutralizes; Add hydrochloric acid while stirring and measure the pH value simultaneously, when pH reaches 4.4-4.6, stop to add hydrochloric acid, the circulation cool brine that at this moment freon refrigerator is produced is sent into the cooling of crystallization kettle interlayer; The filtrating temperature remains on 0 ℃-3 ℃ in the control still; Under this temperature, slowly stir crystallization in 12 hours, after crystallization finishes all materials are sent into whizzer elimination filtrating, obtain first N-acetyl-L-tyrosine bullion; Obtain filtrating and return concentration tank, sent into the crystallization kettle crystallisation by cooling once more 12 hours after being concentrated into half of volume, obtain second batch of N-acetyl-L-tyrosine bullion, first is merged with second batch of bullion use; Step (3) is sent N-acetyl-L-tyrosine bullion into reaction kettle, adds rising temperature for dissolving behind an amount of pure water, adds gac when being heated to 70 ℃; Constant temperature stirs decolouring 0.5 hour, obtains clear liquid after using 0.5 square metre of half frame to filter then, with the clear liquid that obtains squeeze into refining in and still; The stillness of night, when being cooled to 0-3 ℃, constant temperature kept crystallization in 12 hours through in refining, feeding the circulation refrigerated brine with the still interlayer behind the naturally cooling; Crystallisate after the crystallization is sent into whizzer and is filtered; Promptly obtain the wet article of N-acetyl-L-tyrosine, the article of wetting are sent into negative pressure oven dry in the dryer, bake out temperature is 50 ℃-56 ℃; Drying time is 4-5 hour, and the caking thing pulverizing back dress after will drying then wraps into the storehouse and gets product.
2. the working method of a kind of N-acetyl according to claim 1-L-tyrosine, the characteristic of its step (1) is: the described acetylizad reaction times of L-tyrosine is 2 hours.
3. the working method of a kind of N-acetyl according to claim 1-L-tyrosine, the characteristic of its step (3) is: when described bake out temperature was 50 ℃, drying time was 5 hours; When bake out temperature was 53 ℃, drying time was 4.5 hours; When bake out temperature was 56 ℃, drying time was 4 hours.
4. the method for use of N-acetyl-L-tyrosine is: use as meticulous organic chemical industry's midbody.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111153829A (en) * | 2019-12-26 | 2020-05-15 | 烟台鲁银药业有限公司 | Preparation method of N-acetyl-L-tyrosine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153829A (en) * | 2019-12-26 | 2020-05-15 | 烟台鲁银药业有限公司 | Preparation method of N-acetyl-L-tyrosine |
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Application publication date: 20121219 |