CN108658895A - A kind of method of purification of methylenum careuleum - Google Patents
A kind of method of purification of methylenum careuleum Download PDFInfo
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- CN108658895A CN108658895A CN201810373407.7A CN201810373407A CN108658895A CN 108658895 A CN108658895 A CN 108658895A CN 201810373407 A CN201810373407 A CN 201810373407A CN 108658895 A CN108658895 A CN 108658895A
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- methylenum careuleum
- purification
- sodium
- alkali
- acid blue
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/20—[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to biological stain reagent synthesis purification technique fields, especially a kind of method of purification of methylenum careuleum, metathesis reaction occurs with sodium bicarbonate, sodium carbonate mixture by the zinc chloride ingredient in dyestuff alkali acid blue BB, generate zinc carbonate not soluble in water, zinc carbonate sediment is filtered off, concentrated hydrochloric acid is added in filtrate, acicular crystal, leaching crystallization is precipitated, centrifuge dripping, it is dry that the acicular methylenum careuleum of bright green crystallizes.The present invention selects sodium bicarbonate, sodium carbonate mixture to remove zinc method of purification, and method is general easy, and raw material is sufficient, and operation plasticity is big, easy.
Description
Technical field
The present invention relates to biological stain reagent synthesis purification field, specific field is a kind of purification side of high-purity methylenum careuleum
Method.
Background technology
Methylenum careuleum also known as methylenum careuleum, Desmoidpillen, alkali acid blue.
Structural formula is：
Methylenum careuleum is shinny bottle green acicular crystal, is dissolved in water, is slightly dissolved in ethyl alcohol, and solution is in sky blue.
Methylenum careuleum is widely used, and is used as nuclear staining agent in histology, and nerve fiber visitain use and eosin are together
It dyeing and uses as blood, drug is used in fungicide, antidote, oxidation-reduction indicator in chemical analysis, adsorption indicator, with
And the various metals such as mercury, tin measure.
It is to pass through what is purified except zinc using industrial dye alkali acid blue BB as primary raw material to analyze pure methylenum careuleum.
Industrial dye alkali acid blue BB is the double salt of a kind of double salt, i.e. methylenum careuleum and zinc chloride composition, and concrete structure formula is：
Industrial dye alkali acid blue BB is mainly used for the dyeing of cotton, acrylic fibers, fiber crops, silk, is also used for paper coloring, bamboo and wood
Color and manufacture ink and color lake.
It is smaller due to containing solubility in zinc chloride and double salt water in industrial dye alkali acid blue BB, especially in alcohol
Middle smaller, therefore it is not suitable for biological stain and drug therapy.
Prepare high-purity methylenum careuleum, it is necessary to remove the zinc chloride in industrial dye alkali acid blue BB.
It can be aoxidized after being heated due to dyestuff alkali acid blue BB aqueous solutions, depth oxygen is especially more easy under basic conditions
Change, necessarily there is the Methyl Homologue of a small amount of lower level to generate, mainly reddish black A and reddish black B, concrete structure formula are respectively：
Since the polychrome methylene blue of the reddish black B of reddish black A exists, the quality of methylenum careuleum is inherently influenced.
Invention content
It is an object of the invention to prepare a kind of methylenum careuleum of high-content, using sodium bicarbonate, sodium carbonate mixed precipitant
Except zinc method, provide that a kind of reaction condition is wide, and purity is high, yield is high, the method for purification of the good methylenum careuleum of quality stability, to solve
The big problem of the quality control difficulty of high-purity methylenum careuleum is prepared in the prior art.
To achieve the above object, the present invention provides the following technical solutions：
A kind of method of purification of methylenum careuleum, specifically by dyestuff alkali acid blue BB zinc chloride ingredient and sodium bicarbonate,
Metathesis reaction occurs for sodium carbonate mixture, generates zinc carbonate not soluble in water, filters off zinc carbonate sediment, is added in filtrate
Acicular crystal is precipitated in concentrated hydrochloric acid, and leaching crystallizes, centrifuge dripping, dry that the acicular methylenum careuleum of bright green crystallizes.
A kind of method of purification of methylenum careuleum of the present invention, specifically includes following steps：
(1) alkali acid blue BB and water are put into container, is heated to 60~90 DEG C, is gradually added into bicarbonate under stiring
Sodium, sodium carbonate mixture, pH is 7.5~9 for control, after adding, keeps the temperature 30~100 minutes；
(2) it is pressed into lautertuns by filter, filtrate enriching hydrochloric acid is precipitated with light at methylenum careuleum hydrochloride, natural cooling
The bottle green crystallization in pool, centrifuge drying, the methylenum careuleum of dry high-purity.
The method of purification of a kind of methylenum careuleum of the present invention, wherein alkali acid blue BB's and water in the step (1)
Weight ratio is 1:13~16.
The method of purification of a kind of methylenum careuleum of the present invention, wherein alkali acid blue BB and carbonic acid in the step (1)
The weight ratio of hydrogen sodium is 1:0.25~0.35.
The method of purification of a kind of methylenum careuleum of the present invention, wherein the quality of the sodium carbonate in the step (1) is carbon
The 0.1~2% of sour hydrogen sodium quality.
The method of purification of a kind of methylenum careuleum of the present invention, wherein in the step (2), concentrated hydrochloric acid is added in filtrate
When, the weight ratio of alkali acid blue BB and concentrated hydrochloric acid is 1:0.4~0.6.
Compared with prior art, the beneficial effects of the invention are as follows：The present invention selects sodium bicarbonate, sodium carbonate mixture to remove zinc
Method of purification, method is general easy, and raw material is sufficient, and operation plasticity is big, easy.Advantage is that production capacity is substantially improved, and purity is high,
Yield is high, stable quality.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of method of purification of methylenum careuleum：
By raw material alkali acid blue BB 150g, adds water 2250g, when being heated to 60~90 DEG C, carbonic acid is added gradually under stiring
Hydrogen sodium, sodium carbonate mixture (40g sodium bicarbonates add 0.8g sodium carbonate, are dissolved in 500ml water), control reaction solution pH 7.5~
It adds within 9, about 30 minutes, after keeping the temperature 30 minutes, is entered in crystallization tank by filter.Filtrate adds hydrochloric acid 75g, after stirring 15 minutes,
It is allowed to cool and glossiness bottle green crystallization is precipitated.Centrifugal drying is crystallized, methylenum careuleum 64.1g, content >=98.5%, yield are obtained
90.7%.As a result meet pharmacopoeial requirements, significantly larger than analysis methylenum careuleum content's index.
Embodiment 2
A kind of method of purification of methylenum careuleum：
By raw material alkali acid blue BB 150g, adds water 1950g, when being heated to 60~90 DEG C, carbonic acid is added gradually under stiring
Hydrogen sodium, sodium carbonate mixture (40g sodium bicarbonates add 0.04g sodium carbonate, are dissolved in 500ml water), control reaction solution pH 7.5~
It adds within 9, about 30 minutes, heat preservation after sixty minutes, is entered by filter in crystallization tank.Filtrate adds hydrochloric acid 60g, after stirring 15 minutes,
It is allowed to cool and glossiness bottle green crystallization is precipitated.Centrifugal drying is crystallized, methylenum careuleum 63.6g, content >=98.6%, yield are obtained
90%.As a result meet pharmacopoeial requirements, significantly larger than analysis methylenum careuleum content's index.
Embodiment 3
A kind of method of purification of methylenum careuleum：
By raw material alkali acid blue BB 150g, adds water 2400g, when being heated to 60~90 DEG C, carbonic acid is added gradually under stiring
Hydrogen sodium, sodium carbonate mixture (52.5g sodium bicarbonates add 0.8g sodium carbonate, are dissolved in 500ml water), reaction solution pH is 7.5 for control
It adds within~9, about 30 minutes, after keeping the temperature 100 minutes, is entered in crystallization tank by filter.Filtrate adds hydrochloric acid 90g, stirs 15 minutes
Afterwards, it is allowed to cool and glossiness bottle green crystallization is precipitated.Centrifugal drying is crystallized, methylenum careuleum 64.5g is obtained, content >=98.5% is received
Rate 91.3%.As a result meet pharmacopoeial requirements, significantly larger than analysis methylenum careuleum content's index.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of method of purification of methylenum careuleum, it is characterised in that：By the zinc chloride ingredient and bicarbonate in dyestuff alkali acid blue BB
Metathesis reaction occurs for sodium, sodium carbonate mixture, generates zinc carbonate not soluble in water, zinc carbonate sediment is filtered off, in filtrate
Concentrated hydrochloric acid is added, acicular crystal is precipitated, leaching crystallizes, centrifuge dripping, dry that the acicular methylenum careuleum of bright green crystallizes.
2. a kind of method of purification of methylenum careuleum according to claim 1, which is characterized in that specifically include following steps：
(1) alkali acid blue BB and water are put into container, are heated to 60~90 DEG C, be gradually added under stiring sodium bicarbonate,
Sodium carbonate mixture, pH is 7.5~9 for control, after adding, keeps the temperature 30~100 minutes；
(2) it is pressed into lautertuns by filter, filtrate enriching hydrochloric acid is precipitated glossiness at methylenum careuleum hydrochloride, natural cooling
Bottle green crystallizes, centrifuge drying, the methylenum careuleum of dry high-purity.
3. a kind of method of purification of methylenum careuleum according to claim 2, it is characterised in that：Alkali in the step (1)
The weight ratio of acid blue BB and water is 1:13~16.
4. a kind of method of purification of methylenum careuleum according to claim 3, it is characterised in that：Alkali in the step (1)
The weight ratio of acid blue BB and sodium bicarbonate is 1:0.25~0.35.
5. a kind of method of purification of methylenum careuleum according to claim 4, it is characterised in that：Carbonic acid in the step (1)
The quality of sodium is the 0.1~2% of sodium bicarbonate quality.
6. a kind of method of purification of methylenum careuleum according to claim 5, it is characterised in that：In the step (2), in filtrate
When concentrated hydrochloric acid is added, the weight ratio of alkali acid blue BB and concentrated hydrochloric acid is 1:0.4~0.6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810373407.7A CN108658895B (en) | 2018-04-24 | 2018-04-24 | Purification method of methylene blue |
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| CN201810373407.7A CN108658895B (en) | 2018-04-24 | 2018-04-24 | Purification method of methylene blue |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006032879A2 (en) * | 2004-09-23 | 2006-03-30 | Wista Laboratories Ltd. | Methods of chemical synthesis and purification of diaminophenothiazinium compounds including methylthioninium chloride (mtc) |
| CN1970548A (en) * | 2006-12-15 | 2007-05-30 | 贵州同济堂制药有限公司 | Medicinal methylene blue synthesis method |
-
2018
- 2018-04-24 CN CN201810373407.7A patent/CN108658895B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006032879A2 (en) * | 2004-09-23 | 2006-03-30 | Wista Laboratories Ltd. | Methods of chemical synthesis and purification of diaminophenothiazinium compounds including methylthioninium chloride (mtc) |
| CN103012315A (en) * | 2004-09-23 | 2013-04-03 | 卫思道制药有限公司 | Methods of chemical synthesis and purification of diaminophenothiazinium compounds including methylthioninium chloride (MTC) |
| CN1970548A (en) * | 2006-12-15 | 2007-05-30 | 贵州同济堂制药有限公司 | Medicinal methylene blue synthesis method |
Non-Patent Citations (1)
| Title |
|---|
| 张国玺: "药用亚甲蓝生产工艺的研究", 《首都师范大学学报(自然科学版)》 * |
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