CN1569818A - Process for preparing D-tyrosine - Google Patents
Process for preparing D-tyrosine Download PDFInfo
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- CN1569818A CN1569818A CN 200410018049 CN200410018049A CN1569818A CN 1569818 A CN1569818 A CN 1569818A CN 200410018049 CN200410018049 CN 200410018049 CN 200410018049 A CN200410018049 A CN 200410018049A CN 1569818 A CN1569818 A CN 1569818A
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Abstract
The invention discloses a process for preparing D-tyrosine which comprises, subjecting the DL-tyrosine to esterification derivatizing to obtain DL-tyrosine ester, using the hydroxylated acid with optical activity as resolution agent in pure alcohol dissolvent to react with the DL-tyrosine ester, obtaining tyrosine ester hydroxylated salts as diastereomers each other, hydrolyzing the tyrosine ester hydroxylated salt and removing the resolution agent, and expelling ester group.
Description
Technical field
The present invention relates to the amino acid whose preparation method of D type, particularly, obtain the method for D-tyrosine about using chemical resolving agent resolution of racemates tyrosine.
Background technology
Tyrosine has another name called pantonine to hydroxyphenylpropionic acid, para hydroxybenzene L-Ala.English by name Tyrosine, propinic acid, 3-(the 4-hydroxyphenyl)-L-Alanine of or α-Amino-β-(p-hydroxyphenyl).Tyrosine is a kind of typical neutral amino acids (amino identical with carboxyl quantity), has a chiral centre in the molecular structure, thereby has the existence of a pair of enantiomorph, i.e. and L type and D type tyrosine, its structure is shown below:
L (-)-tyrosine D (+)-tyrosine
L-tyrosine is a kind of natural amino acid, its performance is familiar with by people very early, has in fields such as medicine, food, chemical industry so far quite widely to use, for example, L-tyrosine can be used as the additive of food, feed, can be used for aminoacids complex transfusion etc. in the medical treatment.D-tyrosine is alpha-non-natural amino acid, and the past is thought useless always.In recent years, along with deepening continuously of scientific research, find that D-tyrosine has the irreplaceable effect of L-tyrosine in vital movement and medication preparation, D-tyrosine has become a kind of chiral source with wide application prospect, promptly can synthesize a series of chiral drugs as chiral precurser, and these chiral drugs have some special effects with it.For example, be precursor with D-tyrosine, the synthetic Atosiban is important tocolytic agent; The synthetic polypeptide has special efficacy in the treatment malignant tumour; The synthetic Anisomycin has protozoacide, resistance type worm, antimycotic, anti-ly swells and ache, prevents and treats effect such as plant mycosis; Can also synthesize the antimicrobial drug that is used for the treatment of mould, mould red bacterium, yeast, parasitic infection; And it is synthetic to lung, central nervous system, liver, joint, endocardium, eye, ear, skin, stomach, antiphlogistic drug that the Urinary system inflammation curative effect is fabulous or the like.At present, these medicines also are in the pharmacologic agent clinical experiment stage mostly, if these medicines can go on the market comprehensively, the demand of D-tyrosine will certainly sharply rise, yet it is reported, the enterprise that does not also have scale operation D-tyrosine at present both at home and abroad, thereby the research and development of acceleration D-tyrosine technology of preparing are very necessary.
So far, about the fractionation technology of preparing of D-tyrosine rarely have report abroad, and domesticly almost do not have.Document (Sealock R.R.Sealock.Structure specificity of tyrosine in ralation tothe metabolic action of ascorbic acid.J.Biol.chem.; 1946; 166 (1): 1～6) report will obtain N-acetyl-DL-tyrosine after the DL-tyrosine acidylate; split with brucine, the D-tyrosine specific rotatory power that obtains is [α] again
25 D=+10.3 (c=4,1N HCl), total recovery is 62-66%.This method can obtain the higher D-tyrosine of optical purity, but the resolving agent brucine costs an arm and a leg, and poisonous, can't realize industrialization.Document (Suzuki Shunichi, Onishi Norimasa.Thermostable5-substituted hydantoin racemase from Microbacterium and use for producingoptically active amino acid.EP 2001-119275 9 Aug 2001) report utilizes optionally catalytic hydrolysis 5-acrinyl glycolylurea raceme of glycolylurea enzyme, generate the D-N-formyltyrosine, the L-5-of racemization simultaneously acrinyl glycolylurea becomes the raceme glycolylurea, at last with the D-N-formyltyrosine under the effect of lytic enzyme, deacylated tRNA amine generates D-tyrosine.But the enzyme resolution process is comparatively complicated, generally need derive, take off processes such as derivating agent, and the good enzyme of specificity is difficult to obtain, and enzyme loses activity easily, these effects limit the application of enzyme Split Method.
Summary of the invention
The objective of the invention is to research and develop a kind of new method for splitting, to obtain optically pure D-tyrosine at the existing defective of above-mentioned fractionation DL tyrosine.
The technical solution used in the present invention is: the preparation method of D-tyrosine obtains the DL-tyrosine ester after it is characterized in that the esterification of DL-tyrosine derived; Use alcohol acid as resolving agent in pure alcoholic solvent the DL-tyrosine ester that obtains, reaction generates the tyrosine ester hydroxy-acid salt of diastereomer each other; Ester group is removed in above-mentioned tyrosine ester hydroxy-acid salt hydrolysis, remove resolving agent simultaneously and obtain D-tyrosine.
In the above-mentioned esterification, DL tyrosine generates the tyrosine ester hydrochloride with low-molecular-weight alcohol reaction under the sulfur oxychloride effect, add the ammoniacal liquor neutralization again and obtain the DL-tyrosine ester.
In the above-mentioned resolution reaction, alcohol acid comprises amygdalic acid, oxysuccinic acid and the tartrate with chirality, and chirality tartrate comprises L-desoxalic acid and D-desoxalic acid.
DL-tyrosine ester+tartrate → L-tyrosine ester tartrate+D-tyrosine ester tartrate.
In the above-mentioned resolution reaction, mole (mol) concentration ratio of tartrate resolving agent and DL-tyrosine ester is 1: 3～3: 1.
The solvent that uses is anhydrous alcohols, for example methyl alcohol, ethanol, propyl alcohol or butanols.The DL-tyrosine ester that pure alcohols consumption is 5～10mL/g.
Above-mentioned tyrosine ester hydroxy-acid salt is the tyrosine ester tartrate, and D-tyrosine ester tartrate can and be removed resolving agent at hydrolysis ester group under the alkaline condition and finish simultaneously, and used basic solution is a NaOH solution.
L-tyrosine ester tartrate and D-tyrosine ester tartrate are diastereoisomeric salts each other, and their solubleness in pure alcoholic solvent is variant, utilizes this species diversity that they are separated, thereby obtains D-tyrosine.
The D-tyrosine that adopts aforesaid method to make meets the officinal requirement, specific rotatory power [α]
25 D=+10.6 (c=4,1N HCl) are that the benchmark yield is 25% with D tyrosine in the DL-tyrosine.Adopting technical pure tartrate is inexpensive, the wide material sources of resolving agent, and reclaim easily, can recycle, utilizing each other, tyrosine ester tartrate dissolubility difference in pure alcoholic solvent of diastereomer separates, make the preparation technology of D-tyrosine simple, split to compare with enzyme process and more help suitability for industrialized production.
Embodiment
Embodiment one:
In 250ml exsiccant there-necked flask, add the 100ml dehydrated alcohol, be cooled to-10 ℃, under this temperature, slowly drip the 10ml sulfur oxychloride, between control reaction temperature-10～-5 ℃, dropwise, add 20gDL-tyrosine, after reacting two hours under 20 ℃, in 70～80 ℃ of backflows 1～2 hour, this moment, tyrosine all dissolved.Underpressure distillation boils off whole ethanol, obtains the tyrosine ethyl ester hydrochloride, adds the 100ml deionized water, is cooled to 0 ℃, regulates pH value 8.5～9.0 with 25% ammoniacal liquor, and the crystal of separating out is through suction filtration, and drying obtains the white crystal of class of DL-tyrosine ethyl ester.
Take by weighing DL-tyrosine ethyl ester that 20.9g (0.1mol) prepares previously and 7.5g (0.3mol) tartrate in the 250ml there-necked flask, add the 200ml dehydrated alcohol, be heated to backflow, be incubated half an hour, slowly cool to 0 ℃, stirred two hours, filter, drying obtains diastereoisomeric salt, weighs and measures its specific rotation light value.
To obtain diastereoisomeric salt when recrystallization repeatedly is constant to the specific rotation light value, and add gradually and press in the NaOH solution of 5N, water at normal temperature was separated 15～30 minutes, dripped the HCl solution of 3N, regulated pH value to 5～6, and filtration obtains product D-tyrosine.
Embodiment two:
In 250ml exsiccant there-necked flask, add the 100ml dehydrated alcohol, be cooled to-10 ℃, under this temperature, slowly drip the 10ml sulfur oxychloride, between control reaction temperature-10～-5 ℃, dropwise, add 20gDL-tyrosine, after reacting two hours under 20 ℃, in 70～80 ℃ of backflows 1～2 hour, this moment, tyrosine all dissolved.Underpressure distillation boils off whole ethanol, obtains the tyrosine ethyl ester hydrochloride, adds the 100ml deionized water, is cooled to 0 ℃, regulates pH value 8.5～9.0 with 25% ammoniacal liquor, and the crystal of separating out is through suction filtration, and drying obtains the white crystal of class of DL-tyrosine ethyl ester.
Take by weighing DL-tyrosine ethyl ester that 20.9g (0.1mol) prepares previously and 30g (0.2mol) tartrate in the 250ml there-necked flask, add the 200ml dehydrated alcohol, be heated to backflow, be incubated half an hour, slowly cool to 0 ℃, stirred two hours, filter, drying obtains diastereoisomeric salt, weighs and measures its specific rotation light value.
To obtain diastereoisomeric salt when recrystallization repeatedly is constant to the specific rotation light value, and add gradually in the NaOH solution of 5N, water at normal temperature was separated 15～30 minutes, dripped the HCl solution of 3N, regulated pH value to 5～6, the product D-tyrosine that filtration obtains.
Embodiment three:
In 250ml exsiccant there-necked flask, add the 100ml dehydrated alcohol, be cooled to-10 ℃, under this temperature, slowly drip the 10ml sulfur oxychloride, between control reaction temperature-10～-5 ℃, dropwise, add 20gDL-tyrosine, after reacting two hours under 20 ℃, in 70～80 ℃ of backflows 1～2 hour, this moment, tyrosine all dissolved.Underpressure distillation boils off whole ethanol, obtains the tyrosine ethyl ester hydrochloride, adds the 100ml deionized water, is cooled to 0 ℃, regulates pH value 8.5～9.0 with 25% ammoniacal liquor, and the crystal of separating out is through suction filtration, and drying obtains the white crystal of class of DL-tyrosine ethyl ester.
Take by weighing DL-tyrosine ethyl ester that 20.9g (0.1mol) prepares previously and 30g (0.2mol) tartrate in the 250ml there-necked flask, add the 100ml dehydrated alcohol, be heated to backflow, be incubated half an hour, slowly cool to 0 ℃, stirred two hours, filter, drying obtains diastereoisomeric salt, weighs and measures its specific rotation light value.
To obtain diastereoisomeric salt when recrystallization repeatedly is constant to the specific rotation light value, and add gradually in the NaOH solution of 5N, water at normal temperature was separated 15～30 minutes, dripped the HCl solution of 3N, regulated pH value to 5～6, the product D-tyrosine that filtration obtains.
Embodiment four:
In 250ml exsiccant there-necked flask, add the 100ml anhydrous methanol, be cooled to-10 ℃, under this temperature, slowly drip the 10ml sulfur oxychloride, between control reaction temperature-10～-5 ℃, dropwise, add 20gDL-tyrosine, after reacting two hours under 20 ℃, in 70～80 ℃ of backflows 1～2 hour, this moment, tyrosine all dissolved.Underpressure distillation boils off whole methyl alcohol, obtains tyrosine methyl ester hydrochloride, adds the 100ml deionized water, is cooled to 0 ℃, regulates pH value 8.5～9.0 with 25% ammoniacal liquor, and the crystal of separating out is through suction filtration, and drying obtains the white crystal of class of DL-L-Tyrosine methyl ester.
Take by weighing 19.5g (0.1mol) DL-L-Tyrosine methyl ester and 7.5g (0.05mol) tartrate in the 250ml there-necked flask, add the 200ml anhydrous methanol, be heated to backflow, be incubated half an hour, slowly cool to 0 ℃, stirred two hours, filter, drying obtains diastereoisomeric salt, weighs and measures its specific rotation light value.
Obtain recrystallization of diastereoisomeric salt, add gradually in the NaOH solution of 5N, water at normal temperature was separated 15～30 minutes, dripped the HCl solution of 3N, regulated pH value to 5～6, filtered the solid D-tyrosine that obtains.
Embodiment five:
In 250ml exsiccant there-necked flask, add the 100ml anhydrous methanol, be cooled to-10 ℃, under this temperature, slowly drip the 10ml sulfur oxychloride, between control reaction temperature-10～-5 ℃, dropwise, add 20gDL-tyrosine, after reacting two hours under 20 ℃, in 70～80 ℃ of backflows 1～2 hour, this moment, tyrosine all dissolved.Underpressure distillation boils off whole methyl alcohol, obtains tyrosine methyl ester hydrochloride, adds the 100ml deionized water, is cooled to 0 ℃, regulates pH value 8.5～9.0 with 25% ammoniacal liquor, and the crystal of separating out is through suction filtration, and drying obtains the white crystal of class of DL-L-Tyrosine methyl ester.
Take by weighing 19.5g (0.1mol) DL-L-Tyrosine methyl ester and 7.5g (0.05mol) tartrate in the 250ml there-necked flask, add the 100ml anhydrous methanol, be heated to backflow, be incubated half an hour, slowly cool to 0 ℃, stirred two hours, filter, drying obtains diastereoisomeric salt, weighs and measures its specific rotation light value.
Obtain diastereoisomeric salt when recrystallization repeatedly is constant to the specific rotation light value, add gradually in the NaOH solution of 5N, water at normal temperature was separated 15～30 minutes, dripped the HCl solution of 3N, regulated pH value to 5～6, the solid D-tyrosine that filtration obtains.
Embodiment six:
In 250ml exsiccant there-necked flask, add the 100ml anhydrous methanol, be cooled to-10 ℃, under this temperature, slowly drip the 10ml sulfur oxychloride, between control reaction temperature-10～-5 ℃, dropwise, add 20gDL-tyrosine, after reacting two hours under 20 ℃, in 70～80 ℃ of backflows 1～2 hour, this moment, tyrosine all dissolved.Underpressure distillation boils off whole methyl alcohol, obtains tyrosine methyl ester hydrochloride, adds the 100ml deionized water, is cooled to 0 ℃, regulates pH value 8.5～9.0 with 5% ammoniacal liquor, and the crystal of separating out is through suction filtration, and drying obtains the white crystal of class of DL-L-Tyrosine methyl ester.
Take by weighing 19.5g (0.1mol) DL-L-Tyrosine methyl ester and 5.85g (0.033mol) tartrate in the 250ml there-necked flask, add the 100ml anhydrous methanol, be heated to backflow, be incubated half an hour, slowly cool to 0 ℃, stirred two hours, filter, drying obtains diastereoisomeric salt, weighs and measures its specific rotation light value.
Obtain diastereoisomeric salt through a recrystallization, add gradually in the NaOH solution of 5N system, water at normal temperature was separated 15～30 minutes, dripped the HCl solution of 3N, regulated pH value to 5～6, filtered the solid D-tyrosine that obtains.
Embodiment seven:
In 250ml exsiccant there-necked flask, add the 100ml n-propyl alcohol, be cooled to-10 ℃, under this temperature, slowly drip the 10ml sulfur oxychloride, between control reaction temperature-10～-5 ℃, dropwise, add 20gDL-tyrosine, after reacting two hours under 20 ℃, in 70～80 ℃ of backflows 1～2 hour, this moment, tyrosine all dissolved.Underpressure distillation boils off whole n-propyl alcohols, obtains tyrosine propyl ester hydrochloride, adds the 100ml deionized water, is cooled to 0 ℃, regulates pH value 8.5～9.0 with 25% ammoniacal liquor, and the crystal of separating out is through suction filtration, and drying obtains the white crystal of class of DL-tyrosine propyl ester.
Take by weighing 22.3g (0.1mol) DL-tyrosine propyl ester and 7.5g (0.05mol) tartrate in the 250ml there-necked flask, add the 100ml n-propyl alcohol, be heated to backflow, be incubated half an hour, slowly cool to 0 ℃, stirred two hours, filter, drying obtains diastereoisomeric salt, weighs and measures its specific rotation light value.
Obtain diastereoisomeric salt behind recrystallization repeatedly, add gradually in the NaOH solution of 5N, water at normal temperature was separated 15～30 minutes, dripped the HCl solution of 3N, regulated pH value to 5～6, the solid D-tyrosine that filtration obtains.
Embodiment eight:
In 250ml exsiccant there-necked flask, add the 100ml propyl carbinol, be cooled to-10 ℃, under this temperature, slowly drip the 10ml sulfur oxychloride, between control reaction temperature-10～-5 ℃, dropwise, add 20gDL-tyrosine, after reacting two hours under 20 ℃, in 70～80 ℃ of backflows 1～2 hour, this moment, tyrosine all dissolved.Underpressure distillation boils off whole propyl carbinols, obtains tyrosine butyl ester hydrochloride, adds the 100ml deionized water, is cooled to 0 ℃, regulates pH value 8.5～9.0 with 25% ammoniacal liquor, and the crystal of separating out is through suction filtration, and drying obtains the white crystal of class of DL-tyrosine butyl ester.
Take by weighing 22.3g (0.1mol) DL-tyrosine butyl ester and 7.5g (0.05mol) tartrate in the 250ml there-necked flask, add the 100ml propyl carbinol, be heated to backflow, be incubated half an hour, slowly cool to 0 ℃, stirred two hours, filter, drying obtains diastereoisomeric salt, weighs and measures its specific rotation light value.Obtain diastereoisomeric salt behind recrystallization repeatedly, add gradually in the NaOH solution of 5N, water at normal temperature was separated 15～30 minutes, dripped the HCl solution of 3N, regulated pH value to 5～6, the solid D-tyrosine that filtration obtains.
Claims (10)
1, the preparation method of D-tyrosine obtains the DL-tyrosine ester after it is characterized in that the esterification of DL-tyrosine derived; The DL-tyrosine ester that obtains is made resolving agent with alcohol acid in pure alcoholic solvent, reaction generates the tyrosine ester hydroxy-acid salt of diastereomer each other; Ester group is removed in above-mentioned tyrosine ester hydroxy-acid salt hydrolysis, removes resolving agent simultaneously and obtains D-tyrosine.
2, the preparation method of D-tyrosine according to claim 1 is characterized in that the alcohol acid resolving agent is a tartrate.
3, the preparation method of D-tyrosine according to claim 1 is characterized in that mole (mol) concentration ratio of resolving agent and tyrosine ester is 1: 3～3: 1.
4, the preparation method of D-tyrosine according to claim 1, it is characterized in that dripping thionyl chloride in-10～-5 ℃ absolute alcohol, add DL-tyrosine, after reacting two hours under 20 ℃, refluxed 1～2 hour in 70～80 ℃, remaining alcohol is removed in underpressure distillation, obtains the tyrosine ester hydrochloride.
5, the preparation method of D-tyrosine according to claim 1 is characterized in that the tyrosine ester hydrochloride is added deionized water dissolving, is cooled to 0 ℃, and the ammoniacal liquor with 25% is regulated pH value 8.5～9.0 hydrolysis and separated out the DL-tyrosine ester.
6, the preparation method of D-tyrosine according to claim 1 is characterized in that DL-tyrosine ester and tartrate are dissolved in the pure alcoholic solvent, and reflux, insulation slowly cool to 0 ℃, agitation and filtration, and drying obtains diastereomer tyrosine ester tartrate.
7, the preparation method of D-tyrosine according to claim 1, it is characterized in that diastereomer tyrosine ester tartrate is added in the NaOH solution ordinary-temp hydrolysis 15～30 minutes, the HCl solution of dropping 3N, regulate pH value to 5～6, filter and obtain product D-tyrosine.
8, the preparation method of D-tyrosine according to claim 1 is characterized in that described pure alcoholic solvent is anhydrous methanol, ethanol, n-propyl alcohol and propyl carbinol.
9, the preparation method of D-tyrosine according to claim 1 is characterized in that pure alcoholic solvent consumption is 5～10mL/g DL-tyrosine ester.
10, the preparation method of D-tyrosine according to claim 1 is characterized in that D-tyrosine ester tartrate hydrolysis ester group and remove resolving agent and finish simultaneously in basic solution.
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| CN 200410018049 CN1235871C (en) | 2004-04-29 | 2004-04-29 | Process for preparing D-tyrosine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467539A (en) * | 2019-08-30 | 2019-11-19 | 浙江普洛家园药业有限公司 | The method for splitting of one kind 2,6- dimethyltyrosine ester and its application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110467539A (en) * | 2019-08-30 | 2019-11-19 | 浙江普洛家园药业有限公司 | The method for splitting of one kind 2,6- dimethyltyrosine ester and its application |
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