CN117143152A - High-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt synthesis process - Google Patents
High-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt synthesis process Download PDFInfo
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- CN117143152A CN117143152A CN202311104068.XA CN202311104068A CN117143152A CN 117143152 A CN117143152 A CN 117143152A CN 202311104068 A CN202311104068 A CN 202311104068A CN 117143152 A CN117143152 A CN 117143152A
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- ascorbic acid
- magnesium salt
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- phosphate magnesium
- phosphate
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- ACFGRWJEQJVZTM-LEJBHHMKSA-L Magnesium L-ascorbic acid-2-phosphate Chemical compound [Mg+2].OC[C@H](O)[C@H]1OC(=O)C(OP([O-])([O-])=O)=C1O ACFGRWJEQJVZTM-LEJBHHMKSA-L 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229930003268 Vitamin C Natural products 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000011718 vitamin C Substances 0.000 claims abstract description 15
- 235000019154 vitamin C Nutrition 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 1- (2-hydroxyethyl) -1-methyl guanidine dihydrogen phosphate Chemical compound 0.000 claims abstract description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- POXUQBFHDHCZAD-UHFFFAOYSA-N 2-(2,2-dimethyl-1,3-dioxolan-4-yl)-3,4-dihydroxy-2h-furan-5-one Chemical compound O1C(C)(C)OCC1C1C(O)=C(O)C(=O)O1 POXUQBFHDHCZAD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 7
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 239000003480 eluent Substances 0.000 claims abstract description 4
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 125000006239 protecting group Chemical group 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000013067 intermediate product Substances 0.000 claims abstract description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 11
- 229940071870 hydroiodic acid Drugs 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 17
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 16
- 239000002211 L-ascorbic acid Substances 0.000 description 6
- 235000000069 L-ascorbic acid Nutrition 0.000 description 6
- 229960005070 ascorbic acid Drugs 0.000 description 6
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 235000016709 nutrition Nutrition 0.000 description 4
- 230000000865 phosphorylative effect Effects 0.000 description 4
- 229960003624 creatine Drugs 0.000 description 3
- 239000006046 creatine Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 150000003700 vitamin C derivatives Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 231100000021 irritant Toxicity 0.000 description 2
- 239000002085 irritant Substances 0.000 description 2
- 229940078752 magnesium ascorbyl phosphate Drugs 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HTJNEBVCZXHBNJ-XCTPRCOBSA-H trimagnesium;(2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;diphosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O HTJNEBVCZXHBNJ-XCTPRCOBSA-H 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- 201000004569 Blindness Diseases 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 206010015958 Eye pain Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- MIJPAVRNWPDMOR-ZAFYKAAXSA-N L-ascorbic acid 2-phosphate Chemical compound OC[C@H](O)[C@H]1OC(=O)C(OP(O)(O)=O)=C1O MIJPAVRNWPDMOR-ZAFYKAAXSA-N 0.000 description 1
- RGHNJXZEOKUKBD-QTBDOELSSA-N L-gulonic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-QTBDOELSSA-N 0.000 description 1
- 102000045595 Phosphoprotein Phosphatases Human genes 0.000 description 1
- 108700019535 Phosphoprotein Phosphatases Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- MIJPAVRNWPDMOR-UHFFFAOYSA-N [2-(1,2-dihydroxyethyl)-3-hydroxy-5-oxo-2h-furan-4-yl] dihydrogen phosphate Chemical compound OCC(O)C1OC(=O)C(OP(O)(O)=O)=C1O MIJPAVRNWPDMOR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000028993 immune response Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013622 meat product Nutrition 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000004393 visual impairment Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt synthesis process, which comprises the following steps: taking vitamin C as a raw material, and condensing with acetone under the action of a catalyst to prepare an intermediate product 5, 6-O-isopropylidene-L-ascorbic acid; adding distilled water and pyridine into a reaction kettle, stirring and mixing at a low temperature, introducing nitrogen for protection, adding the 5, 6-O-isopropylidene-L-ascorbic acid in S1, slowly adding 1- (2-hydroxyethyl) -1-methyl guanidine dihydrogen phosphate and KOH solution, keeping the pH value of the reaction solution at 12-13, keeping the reaction for 2-3h, and controlling the temperature at-1-5 ℃; s4, adding dilute hydrochloric acid into the concentrated solution to adjust the pH value to 4.0, standing for 2 hours at room temperature to remove the protecting group, then treating by 732 type cation exchange resin, eluting by 0.2mol/L hydrochloric acid, adding magnesium oxide into the eluent, adding methanol according to 2-4 times of the volume of the concentrated solution for crystallization, decoloring and recrystallizing the crude product by activated carbon, and then drying in vacuum to obtain the L-ascorbic acid-2-phosphate magnesium salt finished product.
Description
Technical Field
The invention relates to the technical field of vitamin C derivatives, in particular to a high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt synthesis process.
Background
VC is a well known nutritional vitamin, and is a necessary nutritional ingredient for humans, livestock, poultry and aquatic products. VC is closely related to enhancing immune response, hormone synthesis, mineral absorption and metabolism. Therefore, VC is also a substance necessary for improving disease resistance, promoting growth and preventing and treating diseases. However, VC is extremely sensitive to light and heat, because the enol-type chemical structure of L-ascorbic acid is easy to release hydrogen (H) atoms, the L-ascorbic acid is easy to be oxidized and damaged under the influence of light, heat and other factors, particularly under the high-temperature illumination condition, the oxidation process is that the reduced VC is oxidized into oxidized VC first, if the VC is further oxidized into diketone gulonic acid, the VC activity is lost, the VC is easy to be damaged during cooking, and particularly, the damage of the VC can be accelerated by low-concentration metal ions under the alkaline condition.
L-ascorbic acid-2-phosphate (also known as vitamin C-2-phosphate, vc-2-phosphate) is a vitamin C derivative with high stability which appears in the international market in recent years, and is prepared by esterification reaction of L-ascorbic acid and a phosphorylating agent. The hydroxyl at the 2-position of the L-ascorbic acid molecule is esterified, so that the L-ascorbic acid molecule has higher tolerance and stability to oxygen, acid and alkali in high temperature, water and air, enters a organism, is hydrolyzed and dephosphorylated to be converted into L-ascorbic acid under the action of phosphatase, and has the same biological activity as vitamin C. Therefore, the method is widely applied to the fields of cultivation, feed and the like.
The magnesium ascorbyl phosphate is used as a derivative of vitamin C, has all the effects of the vitamin C, and overcomes the defects that the vitamin C is afraid of light, heat, metal ions and the like and is easy to oxidize. Can be widely used as a nutrition additive in various reinforced foods, nutrition health care products and beverages. The magnesium ascorbyl phosphate has stable property, has excellent antioxidant quality guarantee effect, can effectively prolong the storage period of foods, and can be used as color-protecting antistaling agent for various canned and bagged foods and meat products and whitening agent in cosmetics.
At present, most of the vitamin C phosphate magnesium is synthesized by adopting a radical protection method in industry, phosphorus oxychloride is used as a phosphorylating reagent, but the phosphorus oxychloride has high toxicity, and volatilized gas is toxic, has irritation and corrosiveness, can stimulate mucous membrane and make eyes painful, splashed into conjunctival sac of eyes, namely necrosis and complete vision loss can occur, and more chloride ions can be brought in by adopting the phosphorus oxychloride, so that great pressure is brought to subsequent treatment and purification.
Accordingly, the inventor has made the above-mentioned problems by keeping the experience of design development and practical production in the related industry for many years, and has studied and improved the prior art and the shortcomings, and has provided a clean, safe and environment-friendly process for synthesizing L-ascorbic acid-2-phosphate magnesium salt, which replaces phosphorus oxychloride with a phosphorylating agent, and has high purity and environment-friendly property, so as to achieve the purpose of having more practical value.
Disclosure of Invention
In order to solve the problems mentioned in the background art, the invention provides a high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt synthesis process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt synthesis process comprises the following steps:
s1, taking vitamin C as a raw material, and condensing with acetone under the action of a catalyst to prepare an intermediate product 5, 6-O-isopropylidene-L-ascorbic acid;
s2, adding distilled water and pyridine into a reaction kettle, stirring and mixing at a low temperature, introducing nitrogen for protection, adding the 5, 6-O-isopropylidene-L-ascorbic acid in the S1, slowly adding 1- (2-hydroxyethyl) -1-methyl guanidine dihydrogen phosphate and KOH solution, keeping the pH value of the reaction solution at 12-13, keeping the reaction time for 2-3 hours, and controlling the temperature at-1-5 ℃;
s3, adding MgCl into the reaction solution of S2 2 ·6H 2 Stirring O in water bath at 20-25deg.C for 1-1.5 hr to obtain yellow precipitate, vacuum filtering to obtain white solid (to remove phosphate), evaporating the filtrate on rotary evaporator, concentrating, and controlling temperatureAt 38-45 ℃;
s4, adding dilute hydrochloric acid into the concentrated solution to adjust the pH value to 4.0, standing for 2 hours at room temperature to remove the protecting group, then treating with 732 type cation exchange resin, eluting with 0.2mol/L hydrochloric acid, adding magnesium oxide into the eluent, and crystallizing by adding methanol according to 2-4 times of the volume of the concentrated solution to obtain a crude product of L-ascorbic acid-2-phosphate magnesium salt;
s5, decoloring and recrystallizing the crude product by using active carbon, and then drying in vacuum to obtain a finished product of the L-ascorbic acid-2-phosphate magnesium salt.
Preferably, the catalyst in the S1 is hydroiodic acid, and when the mass ratio of the acetone to the vitamin C is 15-18:1, the temperature is controlled within the range of 30-40 ℃ and the reaction time is 1.5-2h.
Preferably, the ratio of the hydroiodic acid to the vitamin C is 1.3 to 1.5L:15-18Kg.
Preferably, the mass ratio of the 1- (2-hydroxyethyl) -1-methyl guanidine dihydrogen phosphate to the KOH solution in the S2 is 1.3:2-3.2.
Preferably, the specific surface area of the activated carbon in the S5 is 900-1000m 2 The pore volume is 0.88-1.5L/g, and the average pore diameter is 45-50A.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, 1- (2-hydroxyethyl) -1-methyl guanidine dihydrogen phosphate is used as a phosphorus esterifying agent, hydroiodic acid is used as a catalyst, phosphate is synthesized in one step, and only one step of crystallization is performed by using an organic solvent, besides, no other organic solvent is used, so that the method has high safety and low cost; the 1- (2-hydroxyethyl) -1-methyl guanidine phosphate is used as a phosphorylating reagent to replace phosphorus oxychloride, the 1- (2-hydroxyethyl) -1-methyl guanidine phosphate is almost nontoxic, and is used as a high-efficiency sports functional food additive, so that the effects of quickly supplementing energy and relieving muscle exercise fatigue can be achieved, and compared with creatine containing carboxyl, the 1- (2-hydroxyethyl) -1-methyl guanidine phosphate is not easy to carry out cyclization reaction to generate creatine, so that the 1- (2-hydroxyethyl) -1-methyl guanidine phosphate can carry out phosphorylation reaction to generate an energy substance like creatine, is safe and nontoxic, and can completely replace phosphorus oxychloride.
2. The preparation method provided by the invention reduces the contents of reaction byproducts and unreacted substances, has the advantages of simple preparation method, high safety and low toxic and irritant gas content, effectively controls the chloride index of the finished L-ascorbic acid-2-phosphate magnesium salt, reduces the discharge of waste water, acid and alkali, has high phosphorus oxychloride toxicity, and the volatilized gas is toxic, irritant and corrosive, and can irritate mucous membrane and cause eye pain.
3. In the invention, under the existence of hydroiodic acid, vitamin C reacts with acetone to protect 5, 6-hydroxyl of vitamin C, and after the reaction is finished, the vitamin C reacts with 1- (2-hydroxyethyl) -1-methyl guanidine dihydrogen phosphate and potassium hydroxide in a pyridine aqueous solution system without separation, so that the pH of the reaction solution is maintained at 12-13, the steps are simplified, the yield is improved, the purity of the product is up to more than 98wt%, and the yield of the product is up to more than 88%.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise specified, the raw materials used in the present invention are all derived from conventional products purchased in the market. Wherein vitamin C is purchased from Aribab, ji's Xin Jiulong Biotechnology Co., ltd., CAS number: 2001-9;
acetone was purchased from aladine, CAS number: 67-64-1;
hydroiodic acid was purchased from aledine, CAS number: 10034-85-2;
1- (2-hydroxyethyl) -1-methylguanidine dihydrogen phosphate was purchased from Allatin, CAS number: 6903-79-3;
732 cation exchange resin purchased from aleba, bihong chemical product sales department, county, large, CAS number: 201058-08-4.
Example 1
S1, adding 90L of acetone and 1.3L of hydroiodic acid into a reaction kettle, adding 15.8Kg of vitamin C under stirring, controlling the temperature at 30 ℃ and the reaction time at 1.5h;
s2, adding 150L of distilled water and 37L of pyridine into a reaction kettle, stirring and mixing at a low temperature, introducing nitrogen for protection, adding 5, 6-O-isopropylidene-L-ascorbic acid, slowly adding 1.3Kg of 1- (2-hydroxyethyl) -1-methylguanidine dihydrogen phosphate and 2.5L of KOH solution, keeping the pH value of the reaction solution at 12, keeping the reaction for 2 hours, and controlling the temperature at-1 ℃;
s3, adding 1.2L of MgCl into the reaction solution 2 ·6H 2 O is stirred for 1h in a water bath at 20 ℃, yellow precipitation appears in the reaction liquid, white solid is obtained by suction filtration (to remove phosphate radical), and then filtrate is evaporated and concentrated on a rotary evaporator, and the temperature is controlled at 38 ℃;
s4, adding dilute hydrochloric acid into the concentrated solution to adjust the pH value to 4.0, standing for 2 hours at room temperature to remove the protecting group, then treating with 732 type cation exchange resin, eluting with 0.2mol/L hydrochloric acid, adding 12.5Kg of magnesium oxide into the eluent, and adding methanol according to 2 times of the volume of the concentrated solution for crystallization to obtain a crude product of L-ascorbic acid-2-phosphate magnesium salt;
s5, the crude product is further treated by activated carbon (the specific surface area of the activated carbon is 900 m) 2 The pore volume is 0.88L/g, the average pore diameter is 45A), decoloring and recrystallizing, then vacuum drying to obtain 22.8Kg of L-ascorbic acid-2-phosphate magnesium salt finished product, analyzing and detecting the crystallized product by infrared spectrum and TLC method, and determining the purity of the product by ultraviolet spectrum, wherein the experiment proves that the product has pure color, the purity can reach 98.5wt%, the yield is 88.6%, and the product meets the national industry standard.
Example 2
This embodiment differs from embodiment 1 in that:
the dosage of the hydroiodic acid in the S1 is 1.4L, the temperature is controlled at 35 ℃, and the reaction time is 1.8h;
s2, maintaining the pH value of the reaction solution at 12.5, reacting for 2.5 hours, and controlling the temperature at 1 ℃;
stirring in water bath at 22deg.C for 1.2h in S3, and evaporating and concentrating at 42deg.C;
s4, adding methanol for crystallization according to 3 times of the volume of the concentrated solution;
s5 the specific surface area of the activated carbon is 950m 2 Pore volume of 1.2L/g and average pore diameter of 48A;
the prepared L-ascorbic acid-2-phosphate magnesium salt finished product is 23.2Kg, the purity can reach 98.6wt percent, the yield is 88.7 percent, and the national standard is met.
Other undescribed structures refer to embodiment 1.
Example 3
This embodiment differs from embodiment 1 in that:
the dosage of the hydroiodic acid in the S1 is 1.5L, the temperature is controlled at 40 ℃, and the reaction time is 2h;
s2, maintaining the pH value of the reaction solution at 13, and controlling the temperature at 5 ℃ for 3 hours;
stirring in water bath at 25deg.C for 1.5 hr in S3, and evaporating and concentrating at 45deg.C;
s4, adding methanol for crystallization according to 4 times of the volume of the concentrated solution;
s5 the specific surface area of the activated carbon is 1000m 2 Pore volume of 1.5L/g and average pore diameter of 50A;
22.9Kg of L-ascorbic acid-2-phosphate magnesium salt finished product is prepared, the purity can reach 98.3 weight percent, the yield is 88.4 percent, and the national standard is met.
Other undescribed structures refer to embodiment 1.
According to the embodiment, the L-ascorbic acid-2-phosphate magnesium salt product conforming to GB 1903.24-2016 can be obtained by the synthesis process, phosphorus oxychloride with high pollution and high toxicity is not needed, the synthesis process is environment-friendly, the product purification step is simplified, the product purity is up to more than 98wt%, and the product yield is up to more than 88%, and is greatly improved compared with the prior art.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The synthesis process of the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt is characterized by comprising the following steps of:
s1, taking vitamin C as a raw material, and condensing with acetone under the action of a catalyst to prepare an intermediate product 5, 6-O-isopropylidene-L-ascorbic acid;
s2, adding distilled water and pyridine into a reaction kettle, stirring and mixing at a low temperature, introducing nitrogen for protection, adding the 5, 6-O-isopropylidene-L-ascorbic acid in the S1, slowly adding 1- (2-hydroxyethyl) -1-methyl guanidine dihydrogen phosphate and KOH solution, keeping the pH value of the reaction solution in a certain range, and reacting for 2-3 hours;
s3, adding MgCl into the reaction solution of S2 2 ·6H 2 Stirring O in water bath at 20-25deg.C for 1-1.5 hr to obtain yellow precipitate, vacuum filtering to obtain white solid, and concentrating the filtrate by evaporating on rotary evaporator;
s4, adding dilute hydrochloric acid into the concentrated solution to adjust the pH value to 4.0, standing for 2 hours at room temperature to remove the protecting group, then treating by cation exchange resin, eluting by hydrochloric acid, adding magnesium oxide into the eluent, and crystallizing by methanol to obtain a crude product of L-ascorbic acid-2-phosphate magnesium salt;
s5, decoloring and recrystallizing the crude product by using active carbon, and then drying in vacuum to obtain a finished product of the L-ascorbic acid-2-phosphate magnesium salt.
2. The process for synthesizing the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt according to claim 1, wherein the catalyst is hydroiodic acid, and the reaction time is 1.5-2h when the mass ratio of the acetone to the vitamin C is 15-18:1, and the temperature is controlled within the range of 30-40 ℃.
3. The process for synthesizing the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt according to claim 2, wherein the adding ratio of the hydroiodic acid to the vitamin C is 1.3-1.5mL:15-18g.
4. The process for synthesizing the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt according to claim 1, wherein the pH value in S2 is maintained at 12-13, and the temperature is controlled at-1-5 ℃.
5. The process for synthesizing the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt according to claim 1, wherein the cation exchange resin in the S4 is 732 type cation exchange resin.
6. The process for synthesizing the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt according to claim 1, wherein the mass ratio of the 1- (2-hydroxyethyl) -1-methyl guanidine dihydrogen phosphate to the KOH solution in the S2 is 1.3:2-3.2.
7. The process for synthesizing the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt according to claim 1, wherein the evaporation concentration temperature in the step S3 is controlled to be 38-45 ℃.
8. The process for synthesizing the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt, which is characterized in that the concentration of hydrochloric acid in S4 is 0.2mol/L.
9. The process for synthesizing the high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt according to claim 1, wherein methanol is added into the S4 according to 2-4 times of the volume of the concentrated solution.
10. The process for synthesizing high-purity environment-friendly L-ascorbic acid-2-phosphate magnesium salt according to claim 1, wherein the specific surface area of the activated carbon in S5 is 900-1000m 2 The pore volume is 0.88-1.5L/g, and the average pore diameter is 45-50A.
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