CN101591257A - A kind of preparation method of crystal L-arginine L-aspartate - Google Patents
A kind of preparation method of crystal L-arginine L-aspartate Download PDFInfo
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- CN101591257A CN101591257A CNA2008100381169A CN200810038116A CN101591257A CN 101591257 A CN101591257 A CN 101591257A CN A2008100381169 A CNA2008100381169 A CN A2008100381169A CN 200810038116 A CN200810038116 A CN 200810038116A CN 101591257 A CN101591257 A CN 101591257A
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- Prior art keywords
- arginine
- crystal
- preparation
- aspartate
- solvent
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- 239000013078 crystal Substances 0.000 title claims abstract description 47
- SUUWYOYAXFUOLX-ZBRNBAAYSA-N (2s)-2-aminobutanedioic acid;(2s)-2-amino-5-(diaminomethylideneamino)pentanoic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O.OC(=O)[C@@H](N)CCCN=C(N)N SUUWYOYAXFUOLX-ZBRNBAAYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims abstract description 12
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims abstract description 12
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 12
- 229960005261 aspartic acid Drugs 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000001186 cumulative effect Effects 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims abstract description 9
- 229930064664 L-arginine Natural products 0.000 claims abstract description 9
- 235000014852 L-arginine Nutrition 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005304 joining Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- 239000004475 Arginine Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 3
- 239000002775 capsule Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- -1 amino acid salts Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000020710 ginseng extract Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000008297 liquid dosage form Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of crystal L-arginine L-aspartate, this method comprises: the arginic aqueous solution of preparation L-, slowly the L-aspartic acid is added wherein, and the mol ratio of L-arginine and L-aspartic acid is 1: 1; After dissolving fully, 50～80 ℃ of following concentrating under reduced pressure, the water yield of removing cumulative volume 20%～60% is cooled to 20～30 ℃; Slowly add organic hydrophilic solvent, the perhaps mixed solvent of polar hydrophilic solvent and non-polar solvent; Cooling, crystallization, filtration, washing, vacuum-drying obtain crystal L-arginine L-aspartate.Compared with prior art, technology of the present invention is reasonable, and step is simple, processing ease, the product crystal formation of gained is good, prevented from caking, be convenient to transportation and use, also have purity height (〉=98%), the yield height advantages such as (80～86%) of product simultaneously, be adapted to suitability for industrialized production.
Description
Technical field
The present invention relates to amino acid salts, relate in particular to a kind of preparation method of crystal L-arginine L-aspartate.
Background technology
The L-arginine L-aspartate is a kind of amidates healthcare products that sales volume increases day by day on the present world market, is mainly used in Ginseng Extract, enhances metabolism, strengthens body immunity etc.Growing along with the international market demand amount becomes the emphasis that people pay close attention to the research of the crystallization method of L-arginic acid salt, particularly to the research of the salify crystalline method of L-arginine L-aspartate.
At present, preparation method's complicated operation of crystal L-arginine L-aspartate, yield is low, is not suitable for suitability for industrialized production, can't satisfy growing demand, and product also exists shortcomings such as purity is low, crystal formation is not good simultaneously.
Summary of the invention
Purpose of the present invention is exactly the preparation method that the crystal L-arginine L-aspartate that a kind of technology is reasonable, simple to operate, crystal formation is good is provided for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of crystal L-arginine L-aspartate is characterized in that, this method may further comprise the steps:
(1) the arginic aqueous solution of preparation L-slowly adds the L-aspartic acid in the arginic aqueous solution of L-, and the mol ratio of L-arginine and L-aspartic acid is 1: 1;
(2) fully the dissolving after, 50～80 ℃ of following concentrating under reduced pressure, the water yield of removing cumulative volume 20%～60% is cooled to 20～30 ℃;
(3) slowly add organic hydrophilic solvent, the perhaps mixed solvent of polar hydrophilic solvent and non-polar solvent, the adding total amount is to remove 3～4 times of the volume that anhydrates in the step (2), the joining day is 0.5～2.5 hour;
(4), more after filtration, washing, vacuum-drying, obtain crystal L-arginine L-aspartate with system cooling, crystallization.
The concentration of the arginic aqueous solution of L-is 20%～30% (weight) in the described step (1).
In the described step (2), after dissolving fully, 55 ℃ of following concentrating under reduced pressure, the water yield of removing cumulative volume 30%～40% is cooled to 22～25 ℃.
Organic hydrophilic solvent is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the isopropylcarbinol in the described step (3).
The volume ratio of mixed solvent Semi-polarity hydrophilic solvent and non-polar solvent is 1～5: 1 in the described step (3), described polar hydrophilic solvent is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the isopropylcarbinol, and described non-polar solvent is selected from sherwood oil, the normal hexane a kind of.
The crystalline temperature is 5～10 ℃ in the described step (4).
Vacuum drying temperature is 50～70 ℃ in the described step (4).
The present invention adopts the L-aspartic acid that adds equimolar amount in the L-arginine aqueous solution, at ambient temperature, the reaction salify, then under 50～80 ℃ temperature condition, concentrating under reduced pressure is removed the water that is equivalent to cumulative volume 20～60%, add hydrophilic organic solvent or mixed solvent again, obtain product 20～30 ℃ of crystallizations, reaction formula is as follows:
Product of the present invention can mix with acceptable carrier on one or more protective foodss according to the production method of field of health care food routine, obtains containing the various formulations of L-arginine L-aspartate to the human body significant quantity.The protective foods acceptable carrier is meant conventional protective foods carrier, and for example: thinner, vehicle etc. can also add other assistant agent and flavouring agent, sweeting agent etc. in addition; Its dosage form comprises various solid dosages and liquid dosage form.
Product L-arginine L-aspartate of the present invention is by the crowd by oral administration to this nutritive food of needs.Be used for when oral, can be made into conventional solid preparation such as tablet, pulvis, granule, capsule etc., also can be made into liquid preparation such as water or oiliness suspension agent etc. or other liquid preparation such as syrup etc.; Preferred form is tablet, coated tablet, capsule etc.
Compared with prior art, preparation method's technology of crystal L-arginine L-aspartate of the present invention is reasonable, step is simple, processing ease, the product crystal formation of gained is good, and prevented from caking is convenient to transportation and use, also have purity height (〉=98%), the yield height advantages such as (80～86%) of product simultaneously, be adapted to suitability for industrialized production.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of crystal L-arginine L-aspartate: in the 500ml reaction flask, adding 70ml (69.6g) content is the L-arginine solution (being equivalent to the 0.1molL-arginine) of 25% (weight), stir, slowly add 13.3g (0.1mol) L-aspartic acid, room temperature reaction 10mins, dissolving, concentrating under reduced pressure then fully, 55 ℃ of bath temperatures, the concentration of reaction solution cumulative volume is cooled to 23 ℃ to the 56ml, slowly drips 95% ethanol while stirring when having small amount of crystalline to separate out, stir 10mins, continue then to drip 95% ethanol, the ethanol total amount is 42ml, and the dropping time is 2hr, then the crystal solution temperature is reduced to 5～10 ℃, place 30mins, make crystal structure complete, filter, crystal 95% washing with alcohol, and, obtaining white plates crystal L-arginine L-aspartate (1: 1) 25g 60 ℃ of vacuum-dryings, yield is 81.4%, purity is 99.8%, [α]
D+ 25.9 ° (c=4,6N HCl).
Embodiment 2
A kind of preparation method of crystal L-arginine L-aspartate: in the 500ml reaction flask, adding 70ml (69.6g) content is the L-arginine solution (being equivalent to the 0.08molL-arginine) of 20% (weight), stir, slowly add 10.64g (0.08mol) L-aspartic acid, room temperature reaction 10mins, dissolving, concentrating under reduced pressure then fully, 50 ℃ of bath temperatures, the concentration of reaction solution cumulative volume is cooled to 20 ℃ to the 28ml, slowly drips anhydrous methanol while stirring when having small amount of crystalline to separate out, stir 10mins, continue then to drip anhydrous methanol, the methyl alcohol total amount is 168ml, and the dropping time is 2.5hr, then the crystal solution temperature is reduced to 5～10 ℃, place 30mins, make crystal structure complete, filter, crystal washs with anhydrous methanol, and, obtaining white plates crystal L-arginine L-aspartate (1: 1) 19.7g 50 ℃ of vacuum-dryings, yield is 80.4%, purity is 99.5%, [α]
D+ 26.8 ° (c=4,6N HCl).
Embodiment 3
A kind of preparation method of crystal L-arginine L-aspartate: in the 500ml reaction flask, adding 70ml (69.6g) content is the L-arginine solution (being equivalent to the 0.12molL-arginine) of 30% (weight), stir, slowly add 15.96g (0.12mol) L-aspartic acid, room temperature reaction 10mins, dissolving, concentrating under reduced pressure then fully, 80 ℃ of bath temperatures, the concentration of reaction solution cumulative volume is cooled to 22 ℃ to the 49ml, slowly drips isopropylcarbinol while stirring when having small amount of crystalline to separate out, stir 10mins, continue then to drip isopropylcarbinol, the isopropylcarbinol total amount is 63ml, and the dropping time is 2hr, then the crystal solution temperature is reduced to 5～10 ℃, place 30mins, make crystal structure complete, filter, crystal washs with isopropylcarbinol, and, obtaining white plates crystal L-arginine L-aspartate (1: 1) 30.5g 70 ℃ of vacuum-dryings, yield is 82.8%, purity is 98.6%, [α]
D+ 26.3 ° (c=4,6N HCl).
Embodiment 4
A kind of preparation method of crystal L-arginine L-aspartate: in the 500ml reaction flask, adding 70ml (69.6g) content is the L-arginine solution (being equivalent to the 0.1molL-arginine) of 25% (weight), stir, slowly add 13.3g (0.1mol) L-aspartic acid, room temperature reaction 10mins, dissolving fully, concentrating under reduced pressure then, 55 ℃ of bath temperatures, the concentration of reaction solution cumulative volume is to the 42ml, be cooled to 25 ℃, slowly drip the mixed solvent propyl alcohol while stirring: normal hexane (1: 1), mixed solvent total amount are 112ml, and the dropping time is 0.5hr, then the crystal solution temperature is reduced to 5～10 ℃, place 30mins, make crystal structure complete, filter, crystal washs with above-mentioned mixed solvent, and, obtaining white plates crystal L-arginine L-aspartate (1: 1) 26.4g 60 ℃ of vacuum-dryings, yield is 86.0%, purity is 98.0%, [α]
D+ 27.2 ° (c=4,6N HCl).
Embodiment 5
A kind of preparation method of crystal L-arginine L-aspartate: in the 500ml reaction flask, adding 70ml (69.6g) content is the L-arginine solution (being equivalent to the 0.1molL-arginine) of 25% (weight), stir, slowly add 13.3g (0.1mol) L-aspartic acid, room temperature reaction 10mins, dissolving fully, concentrating under reduced pressure then, 55 ℃ of bath temperatures, the concentration of reaction solution cumulative volume is to the 42ml, be cooled to 30 ℃, slowly drip mixed solvent methyl alcohol while stirring: sherwood oil (5: 1), mixed solvent total amount are 84ml, and the dropping time is 40min, then the crystal solution temperature is reduced to 5～10 ℃, place 30mins, make crystal structure complete, filter, crystal washs with above-mentioned mixed solvent, and, obtaining white plates crystal L-arginine L-aspartate (1: 1) 26.4g 60 ℃ of vacuum-dryings, yield is 86.0%, purity is 99.2%, [α]
D+ 27.2 ° (c=4,6N HCl).
Claims (7)
1. the preparation method of a crystal L-arginine L-aspartate is characterized in that, this method may further comprise the steps:
(1) the arginic aqueous solution of preparation L-slowly adds the L-aspartic acid in the arginic aqueous solution of L-, and the mol ratio of L-arginine and L-aspartic acid is 1: 1;
(2) fully the dissolving after, 50～80 ℃ of following concentrating under reduced pressure, the water yield of removing cumulative volume 20%～60% is cooled to 20～30 ℃;
(3) slowly add organic hydrophilic solvent, the perhaps mixed solvent of polar hydrophilic solvent and non-polar solvent, the adding total amount is to remove 3～4 times of the volume that anhydrates in the step (2), the joining day is 0.5～2.5 hour;
(4), more after filtration, washing, vacuum-drying, obtain crystal L-arginine L-aspartate with system cooling, crystallization.
2. the preparation method of a kind of crystal L-arginine L-aspartate according to claim 1 is characterized in that, the concentration of the arginic aqueous solution of L-is 20%～30% (weight) in the described step (1).
3. the preparation method of a kind of crystal L-arginine L-aspartate according to claim 1 is characterized in that, in the described step (2), fully after the dissolving, 55 ℃ of following concentrating under reduced pressure, the water yield of removing cumulative volume 30%～40% is cooled to 22～25 ℃.
4. the preparation method of a kind of crystal L-arginine L-aspartate according to claim 1 is characterized in that, organic hydrophilic solvent is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the isopropylcarbinol in the described step (3).
5. the preparation method of a kind of crystal L-arginine L-aspartate according to claim 1, it is characterized in that, the volume ratio of mixed solvent Semi-polarity hydrophilic solvent and non-polar solvent is 1～5: 1 in the described step (3), described polar hydrophilic solvent is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the isopropylcarbinol, and described non-polar solvent is selected from sherwood oil, the normal hexane a kind of.
6. the preparation method of a kind of crystal L-arginine L-aspartate according to claim 1 is characterized in that, the crystalline temperature is 5～10 ℃ in the described step (4).
7. the preparation method of a kind of crystal L-arginine L-aspartate according to claim 1 is characterized in that, vacuum drying temperature is 50～70 ℃ in the described step (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100381169A CN101591257B (en) | 2008-05-27 | 2008-05-27 | Preparation method of crystal L-arginine L-aspartate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100381169A CN101591257B (en) | 2008-05-27 | 2008-05-27 | Preparation method of crystal L-arginine L-aspartate |
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| Publication Number | Publication Date |
|---|---|
| CN101591257A true CN101591257A (en) | 2009-12-02 |
| CN101591257B CN101591257B (en) | 2013-08-07 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102102118B (en) * | 2009-12-18 | 2012-08-15 | 上海汉飞生化科技有限公司 | Method for preparing L-ornithine-L-aspartate salt |
| CN105935139A (en) * | 2015-11-18 | 2016-09-14 | 浙江荣信生物科技有限公司 | L-arginine-L-aspartate and preparation technology thereof |
| CN108689887A (en) * | 2018-04-23 | 2018-10-23 | 宜兴市前成生物有限公司 | A kind of method of industrialized production L-arginine-ASPARTIC ACID |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227007A (en) * | 1990-09-28 | 1993-07-13 | Kyowa Hakko Kogyo Co., Ltd. | Process for producing crystals of salt of acidic amino acid and basic amino acid |
-
2008
- 2008-05-27 CN CN2008100381169A patent/CN101591257B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227007A (en) * | 1990-09-28 | 1993-07-13 | Kyowa Hakko Kogyo Co., Ltd. | Process for producing crystals of salt of acidic amino acid and basic amino acid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102102118B (en) * | 2009-12-18 | 2012-08-15 | 上海汉飞生化科技有限公司 | Method for preparing L-ornithine-L-aspartate salt |
| CN105935139A (en) * | 2015-11-18 | 2016-09-14 | 浙江荣信生物科技有限公司 | L-arginine-L-aspartate and preparation technology thereof |
| CN108689887A (en) * | 2018-04-23 | 2018-10-23 | 宜兴市前成生物有限公司 | A kind of method of industrialized production L-arginine-ASPARTIC ACID |
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| CN101591257B (en) | 2013-08-07 |
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