CN102718833A - Preparation method of glycyl-tyrosine - Google Patents
Preparation method of glycyl-tyrosine Download PDFInfo
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- CN102718833A CN102718833A CN2012101518381A CN201210151838A CN102718833A CN 102718833 A CN102718833 A CN 102718833A CN 2012101518381 A CN2012101518381 A CN 2012101518381A CN 201210151838 A CN201210151838 A CN 201210151838A CN 102718833 A CN102718833 A CN 102718833A
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- tyrosine
- glycyl
- controlled
- temperature
- water
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- XBGGUPMXALFZOT-VIFPVBQESA-N Gly-Tyr Chemical compound NCC(=O)N[C@H](C(O)=O)CC1=CC=C(O)C=C1 XBGGUPMXALFZOT-VIFPVBQESA-N 0.000 title claims abstract description 31
- 108010087823 glycyltyrosine Proteins 0.000 title claims abstract description 31
- XBGGUPMXALFZOT-UHFFFAOYSA-N glycyl-L-tyrosine hemihydrate Natural products NCC(=O)NC(C(O)=O)CC1=CC=C(O)C=C1 XBGGUPMXALFZOT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims abstract description 9
- 229960004441 tyrosine Drugs 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- GDOGSOZOUAVIFX-VIFPVBQESA-N (2s)-2-[(2-chloroacetyl)amino]-3-(4-hydroxyphenyl)propanoic acid Chemical compound ClCC(=O)N[C@H](C(=O)O)CC1=CC=C(O)C=C1 GDOGSOZOUAVIFX-VIFPVBQESA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 238000005915 ammonolysis reaction Methods 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- 238000007098 aminolysis reaction Methods 0.000 abstract 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000001014 amino acid Nutrition 0.000 description 6
- 150000001413 amino acids Chemical class 0.000 description 6
- 108090000765 processed proteins & peptides Proteins 0.000 description 6
- 229940024606 amino acid Drugs 0.000 description 5
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 5
- 238000001727 in vivo Methods 0.000 description 3
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 235000016236 parenteral nutrition Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 108010016626 Dipeptides Proteins 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of glycyl-tyrosine, which comprises the following steps: using L-tyrosine, toluene and water raw material, adding chloroacetamide and sodium hydroxide drop by drop under certain condition, adding hydrochloric acid drop by drop to control the pH value after reacting, then carrying out an aminolysis at normal pressure, heating and concentrating, washing and centrifuging to obtain the glycyl-tyrosine crude product, dissolving, filtering, crystallizing, carrying out pumping filtration and drying to obtain glycyl-tyrosine. The glycyl-tyrosine crystal prepared by the preparation method has high purity, and is beneficial to further purifying and refining glycyl-tyrosine.
Description
Technical field
The invention belongs to chemical technology field, particularly the preparation method of glycyl-tyrosine.
Background technology
The two peptides of the amino acid that uses clinically (15) (2) injection liquid provides amino acid as the parenteral nutrition preparation through parenteral nutrition.Being applied to can not be oral or through enteron aisle supply nutrition, and the nutrition patient that can not satisfy the demand, and particularly is in the metabolic patient of high de-agglomeration.Wherein amino acid exists with two peptide forms of glycyl-Stimulina, glycyl-tyrosine (Glycyl-L-Tyrosine Dihydratc is called for short sweet-junket dipeptides).Two kinds of two peptides (glycyl-Stimulina, glycyl-tyrosine) are used to provide Stimulina and tyrosine to promote proteinic synthesizing.Two peptide species directly are decomposed into glycocoll, Stimulina, three kinds of total free aminoacidss of tyrosine in vivo fully.The two peptides of amino acid (15) (2) injection liquid promotes protein synthesis in vivo and regulates nitrogen equilibrium, makes full use of in vivo for guaranteeing amino acid and two peptide, should give enough energy (glucide, fat), ionogen, trace element and VITAMINs etc. simultaneously.
Preparing method's difficulty of glycyl-tyrosine is high; Patent 200810239035.5 discloses a kind of process for purification of Glycyl-L-tyrosine; Wherein in the Glycyl-L-tyrosine production technology of crude, adopt strong aqua, water, bicarbonate of ammonia, N-chloracetyl-L-tyrosine to generate the Glycyl-L-tyrosine bullion under certain condition, adopt the Glycyl-L-tyrosine bullion yield of this process method preparation low; Cost is high, is not easy to realize industriallization.
Summary of the invention
Goal of the invention: in order to solve above-mentioned technical barrier, the present invention provides a kind of preparation method of glycyl-tyrosine.
The technical scheme that the present invention adopts: a kind of preparation method of glycyl-tyrosine may further comprise the steps:
1, get L tyrosine, toluene, water and be positioned in the vial and stir, external ice-water bath, temperature is controlled at 0～5 ℃; Dropping sodium solution drips process temperature and is controlled at 0～5 ℃, after dropwising, and stirring reaction 30～40 minutes;
2, after upward the step reaction finishes, drip chloroacetyl chloride, while dropping sodium solution, temperature is controlled at-5 ℃～5 ℃, and solution PH is controlled at 11～13;
3, after upward the step dropping finishes, stirred 30～60 minutes, left standstill then 1～2 hour;
4, go up after the step leaves standstill end, liquid is divided into two phases up and down, and lower floor is a water, separates two phases up and down, water is poured in the triangular flask into slow dripping hydrochloric acid, control solution PH=2.5～3.5; Treat that crystal separates out, leave standstill growing the grain after 1～3 hour,, obtain chloracetyl-tyrosine solid through centrifugal, subsequent use;
5, will go up subsequent use chloracetyl-tyrosine solid of step and put into bottle, add bicarbonate of ammonia, water, stirring and dissolving; Heat temperature raising, normal pressure ammonolysis reaction 6～8 hours, temperature is controlled at 40～50 ℃;
6, after going on foot the ammonolysis reaction end on, continue heating and concentrate, temperature is controlled at 70～80 ℃;
7, behind the last EOS, with the liquid concentrator cooling, crystallization is filtered, and Tc is controlled at-5 ℃～10 ℃; The crystal of separating out with organic solvent washing 1～3 time, through centrifugal, is obtained glycyl-tyrosine bullion.
According to the glycyl-tyrosine of above-mentioned steps 7 gained,, comprise dissolving, filtration, crystallization, suction filtration, drying step also through refinement treatment.
Useful effect: synthetic route of the present invention is simple, and supplementary material cheaply is easy to get, and equipment requirements is simple, and the solvent recuperation utilization ratio is high, and cost is low, is easy to realize suitability for industrialized production, can create higher economic value.
Embodiment
Below in conjunction with embodiment the present invention is described further, but protection scope of the present invention is not limited to following embodiment.
Embodiment one
Get L tyrosine 24g, toluene 52g, water 24g and be positioned in the vial and stir, external ice-water bath, temperature is controlled at 0 ℃; Dropping sodium solution drips process temperature and is controlled at 0 ℃, after dropwising, and stirring reaction 30 minutes; Drip chloroacetyl chloride 24g, while dropping sodium solution, temperature is controlled at-5 ℃, and solution PH is controlled at 11; After dripping end, stirred 30 minutes, left standstill then 1 hour; After leaving standstill end, take off a layer water and pour in the triangular flask, slowly dripping hydrochloric acid is controlled solution PH=2.5; Treat that crystal separates out, leave standstill growing the grain after 1 hour, through centrifugal, obtain chloracetyl-tyrosine solid, the chloracetyl-tyrosine solid 38.5g that gets gained puts into the bulb bottle, adds bicarbonate of ammonia 19.5g, water, stirring and dissolving; Heat temperature raising, normal pressure ammonolysis reaction 6 hours, temperature is controlled at 40 ℃; After last step ammonolysis reaction finishes, continue heating and concentrate, temperature is controlled at 70 ℃; With the liquid concentrator cooling, crystallization is filtered then, and Tc is controlled at-5 ℃; The crystal of separating out with organic solvent washing 1 time, through centrifugal, is obtained glycyl-tyrosine bullion, and yield is about 70%.
Embodiment two
Get L tyrosine 240g, toluene 520g, water 240g and be positioned in the vial and stir, external ice-water bath, temperature is controlled at 5 ℃; Dropping sodium solution drips process temperature and is controlled at 5 ℃, after dropwising, and stirring reaction 35 minutes; Drip chloroacetyl chloride 240g, while dropping sodium solution, temperature is controlled at 5 ℃, and solution PH is controlled at 13; After dripping end, stirred 50 minutes, left standstill then 1.5 hours; After leaving standstill end, take off a layer water and pour in the triangular flask, slowly dripping hydrochloric acid is controlled solution PH=3.0; Treat that crystal separates out, leave standstill growing the grain after 2 hours, through centrifugal, obtain chloracetyl-tyrosine solid, the chloracetyl-tyrosine solid 400g that gets gained puts into the bulb bottle, adds bicarbonate of ammonia 200g, water, stirring and dissolving; Heat temperature raising, normal pressure ammonolysis reaction 7 hours, temperature is controlled at 50 ℃; After last step ammonolysis reaction finishes, continue heating and concentrate, temperature is controlled at 80 ℃; With the liquid concentrator cooling, crystallization is filtered then, and Tc is controlled at 10 ℃; The crystal of separating out with organic solvent washing 3 times, through centrifugal, is obtained glycyl-tyrosine bullion, and yield is about 75%.
Embodiment three
Get L tyrosinase 15 00g, toluene 1000g, water 500g and be positioned in the vial and stir, external ice-water bath, temperature is controlled at 2 ℃; Dropping sodium solution drips process temperature and is controlled at 3 ℃, after dropwising, and stirring reaction 40 minutes; Drip chloroacetyl chloride 500g, while dropping sodium solution, temperature is controlled at 0 ℃, and solution PH is controlled at 12; After dripping end, stirred 60 minutes, left standstill then 3 hours; After leaving standstill end, take off a layer water and pour in the triangular flask, slowly dripping hydrochloric acid is controlled solution PH=3.5; Treat that crystal separates out, leave standstill growing the grain after 2 hours, through centrifugal, obtain chloracetyl-tyrosine solid, the chloracetyl-tyrosine solid 800g that gets gained puts into the bulb bottle, adds bicarbonate of ammonia 450g, water, stirring and dissolving; Heat temperature raising, normal pressure ammonolysis reaction 8 hours, temperature is controlled at 45 ℃; After last step ammonolysis reaction finishes, continue heating and concentrate, temperature is controlled at 75 ℃; With the liquid concentrator cooling, crystallization is filtered then, and Tc is controlled at 5 ℃; The crystal of separating out with organic solvent washing 3 times, through centrifugal, is obtained glycyl-tyrosine bullion, and yield is about 80%.
Embodiment four
Get glycyl-tyrosine bullion, add water, use filtering with microporous membrane 50 ℃ of following stirring and dissolving; Under 30 ℃, in filtrating, slowly drip methyl alcohol, stirred 2 hours; Continue to drip methyl alcohol, complete hand to be crystallized, suction filtration; 40 ℃ of decompressions of filter cake (0.09Mpa) dry 5-10 hour, obtain glycyl-tyrosine crystal, yield is about 95%.
Glycyl-tyrosine bullion the yield that adopts above-mentioned process method preparation is at 75-85%, and the glycyl that obtains-tyrosine crystal purity is higher, is beneficial to the further purification of glycyl-tyrosine.
Claims (2)
1. the preparation method of a glycyl-tyrosine is characterized in that: may further comprise the steps:
1), get L-tyrosine, toluene, water and be positioned in the three-necked bottle and stir, external ice-water bath, temperature is controlled at 0～5 ℃; Dropping sodium solution drips process temperature and is controlled at 0～5 ℃, after dropwising, and stirring reaction 30～40 minutes;
2) after, upward the step reaction finishes, drip chloroacetyl chloride, while dropping sodium solution, temperature is controlled at-5 ℃～5 ℃, and solution PH is controlled at 11～13;
3) after, upward the step dropping finishes, stirred 30～60 minutes, left standstill then 1～2 hour;
4), go up after the step leaves standstill end, liquid is divided into two phases up and down, lower floor is a water, separates two phases up and down, water is poured in the triangular flask into slow dripping hydrochloric acid, control solution PH=2.5～3.5; Treat that crystal separates out, leave standstill growing the grain after 1～3 hour,, obtain chloracetyl-tyrosine solid through centrifugal, subsequent use;
5), will go up subsequent use chloracetyl-tyrosine solid of step puts into bottle, adding bicarbonate of ammonia, water, stirring and dissolving; Heat temperature raising, normal pressure ammonolysis reaction 6～8 hours, temperature is controlled at 40～50 ℃;
6), on go on foot ammonolysis reaction and finish after, continue heating and concentrate, temperature is controlled at 70～80 ℃;
7), go up EOS after, with the liquid concentrator cooling, crystallization is filtered, Tc is controlled at-5 ℃～10 ℃; The crystal of separating out with organic solvent washing 1～3 time, through centrifugal, is obtained glycyl-tyrosine.
2. the preparation method of glycyl-tyrosine according to claim 1 is characterized in that: through above-mentioned steps 7) glycyl-tyrosine of gained, also through refinement treatment, comprise dissolving, filtration, crystallization, suction filtration, drying step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101518381A CN102718833A (en) | 2012-05-16 | 2012-05-16 | Preparation method of glycyl-tyrosine |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101518381A CN102718833A (en) | 2012-05-16 | 2012-05-16 | Preparation method of glycyl-tyrosine |
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| CN102718833A true CN102718833A (en) | 2012-10-10 |
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| CN2012101518381A Pending CN102718833A (en) | 2012-05-16 | 2012-05-16 | Preparation method of glycyl-tyrosine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976967A (en) * | 2012-11-13 | 2013-03-20 | 湖北一半天制药有限公司 | Synthesis and study of glycyl-L-tyrosine intermidate |
| CN112552373A (en) * | 2020-12-08 | 2021-03-26 | 河北一品制药股份有限公司 | Industrial preparation method of glycyl-L-tyrosine |
| CN113384523A (en) * | 2021-06-29 | 2021-09-14 | 四川科伦药业股份有限公司 | Production and preparation method of compound amino acid (15) dipeptide (2) injection |
| CN113880911A (en) * | 2021-09-15 | 2022-01-04 | 湖北泓肽生物科技有限公司 | Synthesis method of glycyl-L-tyrosine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6197998B1 (en) * | 1998-04-14 | 2001-03-06 | Kyowa Hakko Kogyo Co., Ltd. | Process for producing N-glycyltyrosine and its crystal structure |
| CN101502639A (en) * | 2009-03-25 | 2009-08-12 | 大连紫萌科技有限公司 | Glycyl-L-tyrosine pharmaceutical formulations and preparation method thereof |
-
2012
- 2012-05-16 CN CN2012101518381A patent/CN102718833A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6197998B1 (en) * | 1998-04-14 | 2001-03-06 | Kyowa Hakko Kogyo Co., Ltd. | Process for producing N-glycyltyrosine and its crystal structure |
| CN101502639A (en) * | 2009-03-25 | 2009-08-12 | 大连紫萌科技有限公司 | Glycyl-L-tyrosine pharmaceutical formulations and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976967A (en) * | 2012-11-13 | 2013-03-20 | 湖北一半天制药有限公司 | Synthesis and study of glycyl-L-tyrosine intermidate |
| CN112552373A (en) * | 2020-12-08 | 2021-03-26 | 河北一品制药股份有限公司 | Industrial preparation method of glycyl-L-tyrosine |
| CN113384523A (en) * | 2021-06-29 | 2021-09-14 | 四川科伦药业股份有限公司 | Production and preparation method of compound amino acid (15) dipeptide (2) injection |
| CN113384523B (en) * | 2021-06-29 | 2022-06-03 | 四川科伦药业股份有限公司 | Production and preparation method of compound amino acid (15) dipeptide (2) injection |
| CN113880911A (en) * | 2021-09-15 | 2022-01-04 | 湖北泓肽生物科技有限公司 | Synthesis method of glycyl-L-tyrosine |
| CN113880911B (en) * | 2021-09-15 | 2023-11-14 | 湖北泓肽生物科技有限公司 | A kind of synthetic method of glycyl-L-tyrosine |
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Application publication date: 20121010 |