CN106117129A - A kind of preparation method of 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. - Google Patents
A kind of preparation method of 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. Download PDFInfo
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- CN106117129A CN106117129A CN201610463654.7A CN201610463654A CN106117129A CN 106117129 A CN106117129 A CN 106117129A CN 201610463654 A CN201610463654 A CN 201610463654A CN 106117129 A CN106117129 A CN 106117129A
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- hydroxymethylpyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/65—One oxygen atom attached in position 3 or 5
- C07D213/66—One oxygen atom attached in position 3 or 5 having in position 3 an oxygen atom and in each of the positions 4 and 5 a carbon atom bound to an oxygen, sulphur, or nitrogen atom, e.g. pyridoxal
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- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention belongs to technical field of organic synthesis, it is specifically related to the preparation method of a kind of 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine., pyridoxine hydrochloride and catalyst are joined in oxidizing agent solution, at uniform temperature, the state response of stirring, sucking filtration, separating catalyst, concentrating under reduced pressure, add pure water, crystallisation by cooling, sucking filtration, wash, air-dry obtain product 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine..The inventive method prepares 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine., and preparation method is simple, and yield is high, and the response time is short, economy, environmental protection, it is easy to industrialized production.
Description
Technical field
The invention belongs to organic synthesis field, particularly relate to the preparation method of a kind of 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine..
Background technology
PLP is used clinically for treating parkinsonism, diabetes, gestation, vomiting, neuritis, liver
The treatment of the diseases such as inflammation, dermatitis and epilepsy.PLP is the coenzyme of the transaminase in amino acid metabolism and decarboxylase,
Glutamic acid decarboxylase can be promoted, promote the generation of γ-aminobutyric acid.
2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. is the important initiation material of synthesis PLP.Prepared 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. by pyridoxine hydrochloride generally to use
The method of oxidation is carried out, and conventional oxidant has manganese oxide, oxygen, hydrogen peroxide etc..
After manganese oxide makees oxidant reaction, containing heavy metal manganese in waste water, its concentration, considerably beyond discharging standards, needs
Could qualified discharge after process.Processing method for this waste water is mainly flocculent precipitation at present, and flocculent precipitation is processed into
This height, effluent quality is unstable, and can produce substantial amounts of slag containing Mn in processing procedure, easily forms secondary pollution the most unrestrained
Take resource.
The by-product of the oxidation reaction rear oxidation agent of hydrogen peroxide oxidation pyridoxine hydrochloride only has water, and reaction is exactly directly environmental protection
Harmless.But the selection of its catalyst and reaction system is crucial.
MoreAshok. (Spectrochimica Acta Part A.Vol.72,2009:204-208) uses price to hold high
Expensive dichloro three (triphenyl phosphorus) ruthenium complex is catalyst, prepares 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. with hydrogen peroxide oxidation pyridoxine hydrochloride.
Chinese patent CN 102617455A (application number: 201110442237.1) discloses in inorganic salt solution with sky
Gas, oxygen, hydrogen peroxide, as oxidant, aoxidize pyridoxine hydrochloride under oxygen-derived free radicals catalyst action and prepare 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine..This
Bright generation a large amount of copper ions waste water, difficult treatment, recycle inconvenience, unfriendly to environment；Introduce amine part and inorganic
Salt so that catalystic converter system is the most complicated, is unfavorable for industrialized production.
Summary of the invention
For solving above-mentioned technical problem, the invention provides that a kind of preparation process is simple, yield is high, the response time is short, ring
The pyridoxine hydrochloride that border is friendly, be prone to industrialized production prepares 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. preparation method.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. preparation method, this preparation method comprises the following steps: by a certain amount of pyridoxine hydrochloride and
Catalyst is dispersed in oxidizing agent solution, then the reaction when stirring, is prepared as pyrrole and trembles after product stirring centrifugal drying
Aldehyde.
Specifically, the amount of described pyridoxine hydrochloride and the material of catalyst is than for 1:0.001～0.005.
As preferably, described catalyst is bismuth tungstate.
Specifically, the amount of described pyridoxine hydrochloride and the material of oxidant is than for 1:10.
As preferably, described oxidant is hydrogen peroxide.
As preferably, the concentration of described hydrogen peroxide is 3%～80%.
As preferably, the reaction temperature of described reaction is 10 DEG C～100 DEG C, and mixing speed is 800～1200rad/min.
As preferably, the response time of described reaction is 1～7h.
The invention have the benefit that preparation method of the present invention is simple, yield is high, and the response time is short, and catalyst can return
Receipts recycle, economy, environmental protection, it is easy to industrialized production.
Detailed description of the invention
Presently in connection with embodiment, the present invention is further detailed explanation.
The reaction equation that the present invention synthesizes 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. is as follows:
Embodiment 1
2.06g (10mmol) pyridoxine hydrochloride, 0.058g (0.05mmol) catalyst tungsten is added in 25mL round-bottomed flask
Acid bismuth and 5mL deionized water, after stirring, add the hydrogen peroxide of 11.5g (35mmol) 30%, in temperature 25 DEG C, stirring speed
Degree is for reacting 1h under 1000rad/min.With high performance liquid chromatography detection pyridoxine hydrochloride conversion ratio and the selection of product 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine.
Property, wherein the conversion ratio of pyridoxol is 97%, and the selection rate of reaction is 98%.
Embodiment 2-6 is substantially the same manner as Example 1, difference such as table 1.
Embodiment 7
Remaining is same as in Example 1 for the preparation method of the 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. of the present embodiment, and difference is: catalyst is for implementing
The catalyst that example 1 reclaims, wherein the conversion ratio of pyridoxol is 97%, and the selection rate of reaction is 98%.
With the above-mentioned desirable embodiment according to the present invention for enlightenment, by above-mentioned description, relevant staff is complete
Entirely can carry out various change and amendment in the range of without departing from this invention technological thought.The technology of this invention
The content that property scope is not limited in description, it is necessary to determine its technical scope according to right.
Claims (8)
1. a 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. preparation method, it is characterised in that this preparation method comprises the following steps: by a certain amount of hydrochloric acid
Pyridoxol and catalyst are dispersed in oxidizing agent solution, then the reaction when stirring, make after product stirring centrifugal drying
Standby one-tenth 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine..
2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. the most according to claim 1 preparation method, it is characterised in that: described pyridoxine hydrochloride and catalysis
The amount of the material of agent is than for 1:0.001～0.005.
2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. the most according to claim 1 preparation method, it is characterised in that: described catalyst is bismuth tungstate.
2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. the most according to claim 1 preparation method, it is characterised in that: described pyridoxine hydrochloride and oxidation
The amount of the material of agent is than for 1:10.
2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. the most according to claim 4 preparation method, it is characterised in that: described oxidant is hydrogen peroxide.
2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. the most according to claim 5 preparation method, it is characterised in that: the concentration of described hydrogen peroxide is
3%～80%.
2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. the most according to claim 1 preparation method, it is characterised in that: the reaction temperature of described reaction is 10
DEG C～100 DEG C, mixing speed is 800～1200rad/min.
2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. the most according to claim 7 preparation method, it is characterised in that: the response time of described reaction is 1
～7h.
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| CN201610463654.7A CN106117129B (en) | 2016-06-23 | 2016-06-23 | A kind of preparation method of pyridoxal |
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| CN201610463654.7A CN106117129B (en) | 2016-06-23 | 2016-06-23 | A kind of preparation method of pyridoxal |
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| CN106117129A true CN106117129A (en) | 2016-11-16 |
| CN106117129B CN106117129B (en) | 2019-05-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382838A (en) * | 2017-08-08 | 2017-11-24 | 东瑞（南通）医药科技有限公司 | A kind of preparation method of phosphopyridoxal pyridoxal phosphate intermediate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617455A (en) * | 2011-12-26 | 2012-08-01 | 浙江工业大学 | Preparation method of pyridoxal or pyridoxal hydrochloride |
-
2016
- 2016-06-23 CN CN201610463654.7A patent/CN106117129B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617455A (en) * | 2011-12-26 | 2012-08-01 | 浙江工业大学 | Preparation method of pyridoxal or pyridoxal hydrochloride |
Non-Patent Citations (4)
| Title |
|---|
| DEEPA G. PATIL，ET AL.: "MECHANISTIC INVESTIGATION OF OXIDATION OF VITAMIN B6 BY DIPERIODATOARGENTATE(III) IN AQUEOUS ALKALINE BY DIPERIODATOARGENTATE(III) IN AQUEOUS ALKALINE", 《WORLD JOURNAL OF PHARMACEUTICAL RESEARCH》 * |
| H AHRENS，ET AL.: "A Direct Method for Preparing Pyridoxal and 4-Pyridoxic Acid", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》 * |
| MORE ASHOK，ET AL.: "Ru(III)-catalyzed oxidation of pyridoxine and albuterol in pharmaceuticals", 《SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY》 * |
| YANHUI ZHANG，ET AL.: "Bi2WO6: A highly chemoselective visible light photocatalyst toward aerobic oxidation of benzylic alcohols in water", 《RSC ADVANCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382838A (en) * | 2017-08-08 | 2017-11-24 | 东瑞（南通）医药科技有限公司 | A kind of preparation method of phosphopyridoxal pyridoxal phosphate intermediate |
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