CN108976259A - A kind of synthetic method of phosphopyridoxal pyridoxal phosphate - Google Patents
A kind of synthetic method of phosphopyridoxal pyridoxal phosphate Download PDFInfo
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- CN108976259A CN108976259A CN201710403181.6A CN201710403181A CN108976259A CN 108976259 A CN108976259 A CN 108976259A CN 201710403181 A CN201710403181 A CN 201710403181A CN 108976259 A CN108976259 A CN 108976259A
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Abstract
The invention discloses a kind of methods for synthesizing phosphopyridoxal pyridoxal phosphate (pyridoxime 5'-phosphate).This method aoxidizes to obtain pyridoxal acid salt by mild reaction condition using pyridoxine hydrochloride as starting material, then carries out phosphating reaction by Phosphation reagent, obtains phosphopyridoxal pyridoxal phosphate.The features such as present invention is easy to get with raw material, and route is simple, and small toxicity, side reaction is few, and product is easily separated, is easy to characterize, and yield is high.
Description
Technical field
The present invention relates to a kind of synthesis fields of pyridoxal acid salt, and in particular to a kind of synthesis side of phosphopyridoxal pyridoxal phosphate
Method.
Background technique
Phosphopyridoxal pyridoxal phosphate (pyridoxime 5'-phosphate, Pyridoxal phosphate, PLP) is the active shape of vitamin B6
Formula.This vitamin mainly includes three kinds of natural organic-compounds: pyridoxal, pyridoxamine and pyridoxol.Phosphopyridoxal pyridoxal phosphate participates in
Several reactions of catalysis have: transamination, α-decarboxylation, β-decarboxylation, β-elimination effect, γ-elimination effect, racemization
Effect and aldol reaction.
The method of chemical synthesis pyridoxal reported in the literature is trembled generally by the oxidation reaction synthesis pyrrole of pyridoxine hydrochloride
Aldehyde, yield is not generally high, and simultaneous reactions process has used a large amount of acid solution, and wastewater flow rate is big, will cause serious environment
Pollution, therefore industrial value is not high.About Phosphation, this step reaction document report is all very simple, and this step reaction document report
Road yield is not high.Therefore significant for industrialized production phosphopyridoxal pyridoxal phosphate to the research of above-mentioned reaction.The present invention proposes
A kind of efficiently mild pyridoxine hydrochloride oxidation reaction method, while passing through optimizing reaction system, the suitable reaction item of control
Part obtains corresponding pyridoxal acid salt, and effective yield reaches 80wt%, while providing a kind of simple and practical phosphopyridoxal pyridoxal phosphate
High-efficiency synthesis method, pyridoxal hydrochloride is further converted to phosphopyridoxal pyridoxal phosphate.
Summary of the invention
The object of the present invention is to provide a kind of efficient and convenient synthetic methods of phosphopyridoxal pyridoxal phosphate, are suitble to industrialized production.
Reaction equation of the invention is as follows:
Wherein [O] is oxidant.
Wherein [P] is phosphoric acid esterification agent.
In first step oxidation reaction, the present invention uses comparatively gentle oxidant such as sodium nitrite, sodium hypochlorite, peroxide
Change hydrogen, hydrogen peroxide urea, activated manganese dioxide, potassium hydrogen persulfate and silver oxide etc., in water or organic solvent, by suitable
Amount acid adjust reaction solution, to pyridoxine hydrochloride (chemical structural formula is shown in reaction equation, chemical name: methyl -3 5- hydroxyl -6-,
4- pyridine diformazan alcohol hydrochloride) carry out oxidation reaction.Organic solvent used in it is acetonitrile, tetrahydrofuran, dioxane, first
Base pyrrolidones etc., the acid used are nitric acid, sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid etc..Reaction condition is mild, and temperature controlling range exists
0-75 DEG C, reaction time range is from 2 hours to 60 hour.Wherein, corresponding acid is added, on the one hand improves reactant hydrochloric acid pyrrole
It trembles pungent solubility, while the oxidation susceptibility of oxidant used in capable of also improving.The main side reaction of reaction is the production generated
Object pyridoxal during the reaction can further occurrence reaction, that is to say, that product pyridoxal is unstable.Store the item of pyridoxal
Part requires to be protected from light low temperature.On the other hand in above-mentioned oxidation reaction process, the methylol of the position 3- of pyridoxine hydrochloride can also occur
Oxidation reaction can generate corresponding by-product.Therefore the control of reaction condition is affected to product yield.
In second step phosphating reaction, the phosphoric acid esterification agent that the present invention uses such as phosphorus oxychloride, phosphorus pentoxide and
85wt% phosphate mixture, phosphorus pentoxide and triethyl phosphate mixture etc. mix that (solvent includes pure with suitable solvent
Water, methylene chloride, chloroform, tetrahydrofuran, dioxane and acetonitrile and its mixture etc.), it is reacted with pyridoxal hydrochloride, most
PH value (4.5~5.5) are adjusted by suitable alkali afterwards, obtain product phosphopyridoxal pyridoxal phosphate.Reaction temperature control range is 0~70
DEG C, reaction time range is from 2 hours to 20 hour.
Synthetic method of the invention includes the following steps:
By weight (solvent/pyridoxine hydrochloride) 4:1~20:1, it is made into pyridoxine hydrochloride solution；(oxidation in molar ratio
Agent/pyridoxine hydrochloride) 1:3~10:1, oxidant is added；The characteristics of according to oxidant, in molar ratio (acid/pyridoxine hydrochloride)
0.5:1~5:1 is added suitable acid, adjusts reacting liquid pH value range, carries out oxidation reaction.Reaction temperature is 0~75 DEG C, instead
It is 2~60h between seasonable.
Above-mentioned oxidant is sodium nitrite (95wt%), sodium hypochlorite (95wt%), hydrogen peroxide (30wt%~
35wt%), hydrogen peroxide urea (95wt%), activated manganese dioxide (85wt%~98.8wt%), potassium hydrogen persulfate
(95wt%) and silver nitrate (95wt%) etc..The organic solvent used is acetonitrile, tetrahydrofuran, dioxane, crassitude
Ketone etc..The acid used is nitric acid, sulfuric acid, hydrochloric acid, acetic acid and phosphoric acid etc..
By solvent and phosphoric acid esterification agent 1:2~5:1 wiring solution-forming in mass ratio；Then (phosphoric acid esterification agent/salt in mass ratio
Sour pyridoxal) 2:1~20:1, pyridoxal hydrochloride is added, adjusts reacting liquid pH value range (4.5~5.5) with aqueous slkali, 0~
30 DEG C are reacted 2 hours to 20 hours.Alkali used includes calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc..
Advantages of the present invention is as follows:
1) reaction raw materials are easy to get, cheap, and synthesis cost is low, have significant economic benefit.
2) reaction condition is mild, and post-processing is simple.
3) water is reduced using suitable organic solvent in reaction system, reduces the generation of sewage significantly.
Specific embodiment
1. oxidant of embodiment is sodium nitrite, and phosphoric acid esterification agent is phosphorus oxychloride
First step oxidation reaction: 15 grams of pyridoxine hydrochlorides and 120 grams of pure water are added in reaction flask, start stirring.It is added 4 grams
30 grams of acetic acid are added at 5 DEG C of reaction temperature in sodium nitrite.Continue to be stirred to react 2 hours at room temperature.Hydrochloric acid is added to adjust
PH value is 4.5.It is concentrated under reduced pressure, 0~5 DEG C of Liquid Residue standing obtains first product.First product is dissolved by heating with ethyl alcohol, active carbon decoloring, weight
Crystallization obtains light yellow to white hydrochloride pyridoxal crystal (yield 80wt%).
Second step phosphating reaction: 30 grams of phosphorus oxychloride is added in reaction flask, starts stirring.Under the conditions of 5 DEG C, delay
The slow pure water for being added dropwise 3 grams, adds 15G tetrahydrofuran.Continue stirring 2 hours.Phosphoric acid esterification agent is obtained, it is spare.Take 10G hydrochloric acid
30G tetrahydrofuran is added in pyridoxal.Then at 0 DEG C hereinafter, being added at one time configured Phosphation reagent.Continue room temperature
It is stirred to react 5 hours.Under the conditions of ice-water bath, reaction solution pH=5.5 is adjusted with sodium hydroxide.Reaction mixture temperature control exists
5 DEG C hereinafter, solid first product is slowly precipitated in stirring.It is filtered under diminished pressure, is dried to obtain solid product (yield 96wt%).
2. oxidant of embodiment is sodium hypochlorite, and phosphoric acid esterification agent is phosphorus pentoxide and 85wt% phosphoric acid
First step oxidation reaction: 15 grams of pyridoxine hydrochlorides and 95 grams of methyl pyrrolidones are added in reaction flask, start stirring.
4.5 grams of sodium hypochlorite are added, at 5 DEG C of reaction temperature, are added 0.65 gram 2,2,6,6- tetramethyl piperidine oxides.At room temperature
Continue to be stirred to react 2 hours.It is 5 that salt acid for adjusting pH value, which is added,.It is concentrated under reduced pressure, 0 DEG C of Liquid Residue standing obtains first product.First product is used
Ethyl alcohol dissolves by heating, active carbon decoloring, and crystallization obtains solid product (yield 80wt%).
Second step phosphating reaction: 15 gram of 85% phosphoric acid and 7.5 grams of phosphorus pentoxides are added in reaction flask, starts and stirs
It mixes, is uniformly mixed.The dioxane of 75G is added.Phosphoric acid esterification agent is obtained, it is spare.It takes 10G to obtain pyridoxal hydrochloride, is added 30G's
Dioxane.Then at 5 DEG C hereinafter, being added at one time configured phosphoric acid esterification agent.Continue that reaction 20 hours is stirred at room temperature.?
Under the conditions of ice-water bath, adjusting reacting liquid pH value with sodium hydroxide aqueous slkali is 5.Reaction mixture temperature control is at 5 DEG C hereinafter, stirring
It mixes and solid first product is slowly precipitated.It is filtered under diminished pressure, is dried to obtain solid product (yield 106wt%).
3. oxidant of embodiment is hydrogen peroxide (35wt% aqueous solution), and phosphoric acid esterification agent is phosphorus pentoxide and tricresyl phosphate
Ethyl ester
First step oxidation reaction: 15 grams of pyridoxine hydrochlorides and 120 grams of water are added in reaction flask, starts stirring.It is added
Secondary 15 grams of aqueous hydrogen peroxide solutions (35wt%) continue to be stirred to react 48 hours at 20 DEG C of reaction temperature.Bisulfite is added
It is complete to determine that excessive hydrogen peroxide consumes by starch potassium iodide paper for sodium.It is concentrated under reduced pressure, salt acid for adjusting pH is added in Liquid Residue
Value is 5, and then ice-water bath is stood, and obtains first product.First product is dissolved by heating with ethyl alcohol, active carbon decoloring, and crystallization obtains solid product
(yield 65wt%).
Second step phosphating reaction: 15 grams of triethyl phosphates and 10 grams of phosphorus pentoxides are added in reaction flask, start
Stirring is uniformly mixed, and 75G tetrahydrofuran is added.It is spare to obtain phosphoric acid esterification agent.It takes 10G to obtain pyridoxal hydrochloride, 30G tetra- is added
Hydrogen furans.Then at 5 DEG C hereinafter, being added at one time configured phosphoric acid esterification agent.Continue that reaction 5 hours is stirred at room temperature.In ice
Under water bath condition, adjusting reacting liquid pH value with sodium hydroxide aqueous slkali is 5.5.Reaction mixture temperature control is at 5 DEG C hereinafter, stirring
It mixes and solid first product is slowly precipitated.It is filtered under diminished pressure, is dried to obtain solid product (yield 90wt%).
4. oxidant of embodiment is hydrogen peroxide urea, and phosphoric acid esterification agent is phosphorus oxychloride
First step oxidation reaction: 15 grams of pyridoxine hydrochlorides and 105 grams of tetrahydrofurans are added in reaction flask, start stirring.
Time 8.5 grams of hydrogen peroxide ureas are added, continue to be stirred to react 15 hours at 40 DEG C of reaction temperature.Sodium hydrogensulfite is added, leads to
It crosses starch potassium iodide paper and determines that excessive hydrogen peroxide consumption is complete.It is concentrated under reduced pressure, Liquid Residue is added salt acid for adjusting pH value and is
5, then 0~5 DEG C of standing, obtains first product.First product is dissolved by heating with ethyl alcohol, active carbon decoloring, and crystallization obtains solid product (yield
60wt%).
Second step phosphating reaction: 30 grams of phosphorus oxychloride is added in reaction flask, starts stirring.Under the conditions of 5 DEG C,
3 grams of pure water is slowly added dropwise, adds 15G tetrahydrofuran.Continue stirring 2 hours.Phosphoric acid esterification agent is obtained, it is spare.Take 10G salt
30G tetrahydrofuran is added in sour pyridoxal.Then at 0 DEG C hereinafter, being added at one time configured Phosphation reagent.Continue room
Temperature is stirred to react 5 hours.Under the conditions of ice-water bath, reaction solution pH=5.5 is adjusted with sodium hydroxide.Reaction mixture temperature control
At 5 DEG C hereinafter, solid first product is slowly precipitated in stirring.It is filtered under diminished pressure, is dried to obtain solid product (yield 96wt%).
5. oxidant of embodiment is activated manganese dioxide, and phosphoric acid esterification agent is phosphorus pentoxide and 85%wt phosphoric acid
First step oxidation reaction: 15 grams of pyridoxine hydrochlorides and 100 grams of water are added in reaction flask, starts stirring.It is added
28.5 grams of hydrochloric acid (37wt%) and 65 grams of activated manganese dioxides (85wt%).Continue to be stirred to react 48 at 55 DEG C of reaction temperature small
When.Unreacted manganese dioxide, filtrate decompression concentration is recovered by filtration, 0 DEG C of Liquid Residue standing obtains first product.First product is added with ethyl alcohol
Heat of solution, active carbon decoloring, crystallization obtain solid product (yield 60wt%).
Second step phosphating reaction: 15 gram of 85% phosphoric acid and 7.5 grams of phosphorus pentoxides are added in reaction flask, starts and stirs
It mixes, is uniformly mixed.The dioxane of 75G is added.Phosphoric acid esterification agent is obtained, it is spare.It takes 10G to obtain pyridoxal hydrochloride, is added 30G's
Dioxane.Then at 5 DEG C hereinafter, being added at one time configured phosphoric acid esterification agent.Continue that reaction 20 hours is stirred at room temperature.?
Under the conditions of ice-water bath, adjusting reacting liquid pH value with sodium hydroxide aqueous slkali is 5.5.Reaction mixture temperature control at 5 DEG C hereinafter,
Solid first product is slowly precipitated in stirring.It is filtered under diminished pressure, is dried to obtain solid product (yield 106wt%).
6. oxidant of embodiment is activated manganese dioxide, and phosphoric acid esterification agent is phosphorus pentoxide and triethyl phosphate
First step oxidation reaction: 15 grams of pyridoxine hydrochlorides and 100 grams of water are added in reaction flask, starts stirring.It is added
28.5 grams of hydrochloric acid (37wt%) and 30 grams of activated manganese dioxides (85wt%).Continue to be stirred to react 48 at 55 DEG C of reaction temperature small
When.Unreacted manganese dioxide is recovered by filtration, the sodium acetate trihydrate and 3 grams of hydroxylamine hydrochloride of 8.5G are added in filtrate.Room
Temperature stirring 1 hour, is obtained by filtration yellow solid.The yellow solid and suitable acidic aqueous solution such as nitric acid, sulfuric acid, hydrochloric acid, vinegar
Acid or phosphoric acid are mixed, and 0 DEG C of solution standing obtains first product.First product is dissolved by heating with ethyl alcohol, and active carbon decoloring, crystallization obtains
Solid product (yield 70wt%).
Second step phosphating reaction: 15 grams of triethyl phosphates and 10 grams of phosphorus pentoxides are added in reaction flask, start
Stirring is uniformly mixed, and 75G tetrahydrofuran is added.It is spare to obtain phosphoric acid esterification agent.10G pyridoxal hydrochloride is taken, 30G tetrahydro is added
Furans.Then at 5 DEG C hereinafter, being added at one time configured phosphoric acid esterification agent.Continue that reaction 5 hours is stirred at room temperature.In ice water
Under the conditions of bath, adjusting reacting liquid pH value with sodium hydroxide aqueous slkali is 4.5.Reaction mixture temperature control is at 5 DEG C hereinafter, stirring
Solid first product is slowly precipitated.It is filtered under diminished pressure, is dried to obtain solid product (yield 90wt%).
7. oxidant of embodiment is potassium hydrogen persulfate, and phosphoric acid esterification agent is phosphorus oxychloride
First step oxidation reaction: 15 grams of pyridoxine hydrochlorides and 100 grams of water are added in reaction flask, starts stirring.It is added 9
Gram potassium hydrogen persulfate.Continue to be stirred to react 20 hours at 40 DEG C of reaction temperature.Suitable sodium hydrogensulfite is added.It depressurizes dense
Contracting, it is 5.5 that a small amount of salt acid for adjusting pH value, which is added, in Liquid Residue, and then 0 DEG C of standing, obtains first product.First product is dissolved by heating with ethyl alcohol, living
Property carbon decoloring, crystallization obtain solid product (yield 35wt%).
Second step phosphating reaction: 30 grams of phosphorus oxychloride is added in reaction flask, starts stirring.Under the conditions of 5 DEG C,
3 grams of pure water is slowly added dropwise, adds 15G tetrahydrofuran.Continue stirring 2 hours.Phosphoric acid esterification agent is obtained, it is spare.Take 10G salt
30G tetrahydrofuran is added in sour pyridoxal.Then at 0 DEG C hereinafter, being added at one time configured Phosphation reagent.Continue room
Temperature is stirred to react 5 hours.Under the conditions of ice-water bath, reaction solution pH=5 is adjusted with sodium hydroxide.Reaction mixture temperature control exists
5 DEG C hereinafter, solid first product is slowly precipitated in stirring.It is filtered under diminished pressure, is dried to obtain solid product (yield 96wt%).
8. oxidant of embodiment is silver oxide, and phosphoric acid esterification agent is phosphorus pentoxide and 85wt% phosphoric acid
First step oxidation reaction: 15 grams of pyridoxine hydrochlorides and 100 grams of water are added in reaction flask, starts stirring.It is added
45 grams of silver oxides.Continue to be stirred to react 50 hours at 65 DEG C of reaction temperature.Unreacted silver oxide, filtrate decompression is recovered by filtration
Concentration, 0 DEG C of Liquid Residue standing, obtains solid product (yield 30wt%).
Second step phosphating reaction: 15 grams of 85wt% phosphoric acid and 7.5 grams of phosphorus pentoxides are added in reaction flask, start
Stirring is uniformly mixed.The dioxane of 75G is added.Phosphoric acid esterification agent is obtained, it is spare.10G pyridoxal hydrochloride is taken, is added 30G's
Dioxane.Then at 5 DEG C hereinafter, being added at one time configured phosphoric acid esterification agent.Continue that reaction 20 hours is stirred at room temperature.?
Under the conditions of ice-water bath, adjusting reacting liquid pH value with sodium hydroxide aqueous slkali is 5.5.Reaction mixture temperature control at 5 DEG C hereinafter,
Solid first product is slowly precipitated in stirring.It is filtered under diminished pressure, is dried to obtain solid product (yield 106wt%).
Claims (10)
1. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate, which is characterized in that specific reaction step are as follows:
(1) pyridoxine hydrochloride solution is prepared, oxidant is added, adds acid, adjusts reacting liquid pH value range, aoxidize anti-
It answers, obtains pyridoxal hydrochloride；
(2) Phosphation agent solution is prepared, the pyridoxal hydrochloride that step (1) obtains is added, the pH value range of solution is adjusted with alkali,
Esterification is carried out, phosphopyridoxal pyridoxal phosphate is obtained.
2. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate as described in claim 1, which is characterized in that prepare hydrochloric acid in step (1)
Benadon solution solvent for use is water, acetonitrile, tetrahydrofuran, dioxane or methyl pyrrolidone, solvent and pyridoxine hydrochloride
Mass ratio be 4:1~20:1.
3. such as a kind of synthetic method of phosphopyridoxal pyridoxal phosphate claimed in claims 1-2, which is characterized in that oxidant in step (1)
For sodium nitrite, sodium hypochlorite, hydrogen peroxide urea, activated manganese dioxide, potassium hydrogen persulfate or silver oxide, oxidant and hydrochloric acid
The molar ratio of Benadon be 1:3~10:1, it is preferable that oxidant be 95wt% sodium nitrite, 95wt% sodium hypochlorite, 30~
35wt% hydrogen peroxide urea, 85~98.8wt% activated manganese dioxide, 95wt% potassium hydrogen persulfate or 95wt% silver oxide.
4. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate as described in claim 1-3, which is characterized in that used in step (1)
Acid is nitric acid, sulfuric acid, hydrochloric acid, acetic acid or phosphoric acid, and the sour molar ratio with pyridoxine hydrochloride is 0.5:1~5:1.
5. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate as described in claim 1-4, which is characterized in that the reaction temperature of step (1)
Degree is 0~75 DEG C, and the reaction time is 2~60h.
6. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate as claimed in claims 1-5, which is characterized in that phosphate in step (2)
Agent be phosphorus oxychloride, the mixture of phosphorus pentoxide and 85wt% phosphoric acid, phosphorus pentoxide and triethyl phosphate mixture,
The mass ratio of phosphoric acid esterification agent and pyridoxal hydrochloride is 2:1~20:1.
7. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate as described in claim 1-6, which is characterized in that prepare phosphorus in step (2)
Esterification agent solution solvent for use is pure water, methylene chloride, chloroform, tetrahydrofuran, dioxane and acetonitrile and its mixing
The mass ratio of object, solvent and Phosphation agent solution is 1:2~5:1.
8. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate as described in claim 1-7, which is characterized in that pH described in step (2)
Being worth range is 4.5~5.5.
9. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate according to claims 1-8, which is characterized in that alkali used in step (2)
For calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
10. a kind of synthetic method of phosphopyridoxal pyridoxal phosphate as claimed in claims 1-9, which is characterized in that the reaction temperature of step (2)
Degree is 0~30 DEG C, and the reaction time is 2~20h.
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| JPS62115286A (en) * | 1985-09-17 | 1987-05-26 | アンステイテユ ナシオナル ド ラ サンテ エ ド ラ ルシエルシユ メデイカル | Enzym insolubilizing method, insolubilized enzyme, novel carrier for enzyme, its production and use of insolubilized enzyme |
| CN1199402A (en) * | 1995-09-04 | 1998-11-18 | 施泰格瓦尔德制药有限公司 | Method for production of magnesium pyridoxal-5'-phosphate glutamate and intermediate products obtained thereby |
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| JPS62115286A (en) * | 1985-09-17 | 1987-05-26 | アンステイテユ ナシオナル ド ラ サンテ エ ド ラ ルシエルシユ メデイカル | Enzym insolubilizing method, insolubilized enzyme, novel carrier for enzyme, its production and use of insolubilized enzyme |
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Address after: 4 / F, building 5, No. 1690, Cailun Road, Shanghai Free Trade Zone Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CATHAY INDUSTRIAL BIOTECH Ltd. Address before: 200120 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 5 No. 1690 Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. |
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Effective date of registration: 20191101 Address after: 4 / F, building 5, No. 1690, Cailun Road, Shanghai Free Trade Zone Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CIBT USA Address before: 201203 floor 4, building 5, No. 1690, Cailun Road, Shanghai pilot Free Trade Zone Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. |
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Application publication date: 20181211 |
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