CN104356102B - A kind of separation method of methyl maltol - Google Patents

A kind of separation method of methyl maltol Download PDF

Info

Publication number
CN104356102B
CN104356102B CN201410545715.5A CN201410545715A CN104356102B CN 104356102 B CN104356102 B CN 104356102B CN 201410545715 A CN201410545715 A CN 201410545715A CN 104356102 B CN104356102 B CN 104356102B
Authority
CN
China
Prior art keywords
methyl maltol
methyl
maltol
barium
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410545715.5A
Other languages
Chinese (zh)
Other versions
CN104356102A (en
Inventor
薛连海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chuzhou University
Original Assignee
Chuzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chuzhou University filed Critical Chuzhou University
Priority to CN201410545715.5A priority Critical patent/CN104356102B/en
Publication of CN104356102A publication Critical patent/CN104356102A/en
Application granted granted Critical
Publication of CN104356102B publication Critical patent/CN104356102B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D309/00Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D309/36Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C07D309/40Oxygen atoms attached in positions 3 and 4, e.g. maltol
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/46Sulfates
    • C01F11/462Sulfates of Sr or Ba

Abstract

The invention provides a kind of separation method of methyl maltol, the methyl maltol in methyl maltol crude product and hydrated barta or barium oxide, selective reaction generates methyl maltol barium.After washing, centrifuging, methyl maltol barium is reacted with sodium sulfate again and generates barium sulfate precipitate and methyl maltol sodium.Again through centrifuging, obtain methyl maltol sodium solution and barium sulfate.Methyl maltol sodium solution, through acidifying, crystallization, centrifuging, obtains methyl maltol solid and aqueous sodium persulfate solution, and methyl maltol solid obtains finished product through recrystallization, oven dry, and metabisulfite solution recycles.Present invention, avoiding high temperature distillation in traditional partition method and cause the carbonization Sum decomposition of methyl maltol, make the yield of methyl maltol bring up to more than 95% from 85%-88%.

Description

A kind of separation method of methyl maltol
Technical field
The present invention relates to chemical field, be specifically related to a kind of separation method of methyl maltol.
Background technology
With furfural and chlorine for the traditional method of main raw material synthesizing methyl voitol is as follows:
1, with MAGNESIUM METAL and methyl chloride for Grignard reagent prepared by raw material.
Mg+CH 3Cl→CH 3MgCl
2, Grignard reagent and furfural through addition, be hydrolyzed and prepare furfuryl alcohol.
3, furfuryl alcohol prepares methyl maltol intermediate through chlorination, rearrangement.
4, methyl maltol intermediate prepares methyl maltol through hydrolysis.
5, synthesize liquid through neutralization, crystallization obtains methyl maltol crude product, methyl maltol crude product through distilling, sublimating, ethyl alcohol recrystallization, obtain methyl maltol finished product.
For above-mentioned steps 5, Traditional Method is separated the main drawback of methyl maltol:
1, methyl maltol crude product is owing to through high temperature oil bath heating sublimation, need cause the carbonization of part methyl voitol, decomposition, and yield is 85%-88%.
2, in sublimation process, the degradation production of methyl maltol is brought in the process of sublimating and product, namely affects the quality of product, causes again certain environmental pollution.
3, owing to adopting high temperature oil bath heating sublimation, need adopt titanium material distillation still, high temperature oil-furnace heating thermal oil is as thermal source, and make equipment, energy expenditure higher, process stability is poor, and there is certain potential safety hazard.
Summary of the invention
For above problems of the prior art, the invention provides that a kind of yield is high, low cost, process stabilization, methyl maltol that security is good separation method.
The present invention is achieved by the following technical solutions:
A separation method for methyl maltol, described separation method comprises the following steps:
1) by methyl maltol crude product and hydrated barta or barium oxide at room temperature, react in the aqueous solution, through suction filtration, washing, methyl maltol barium is obtained;
2) methyl maltol barium step 1 obtained and sodium sulfate at room temperature, react in the aqueous solution, generate methyl maltol sodium and barium sulfate, obtain methyl maltol sodium solution and barium sulfate precipitate through centrifugation; Wherein barium sulfate is through washing, dry as byproduct;
3) methyl maltol sodium solution is through acidifying, crystallization, centrifugation, obtains methyl maltol and aqueous sodium persulfate solution, and methyl maltol obtains finished product through ethyl alcohol recrystallization, oven dry; Aqueous sodium persulfate solution then can be recycled.
Described step 1,2 is all carried out in enamel reaction still.
When adopting hydrated barta, the chemical equation of its synthesis is:
Beneficial effect of the present invention is:
1, in the present invention, the methyl maltol in methyl maltol crude product and hydrated barta or barium oxide, selective reaction generates methyl maltol barium.After washing, centrifuging, methyl maltol barium is reacted with sodium sulfate again and generates barium sulfate precipitate and methyl maltol sodium.Again through centrifuging, obtain methyl maltol sodium solution and barium sulfate.Methyl maltol sodium solution, through acidifying, crystallization, centrifuging, obtains methyl maltol solid and aqueous sodium persulfate solution, and methyl maltol solid obtains finished product through recrystallization, oven dry, and metabisulfite solution recycles.
Present invention, avoiding high temperature distillation in traditional partition method and cause the carbonization Sum decomposition of methyl maltol, make the yield of methyl maltol bring up to more than 95% from 85%-88%.
2, the precipitation conversion process of methyl maltol is all carried out in room temperature, the aqueous solution, mild condition, adopt common enamel reactor, avoid in traditional partition method the equipment that the distillation of titanium material still, high temperature oil-furnace heating etc. must be adopted to bring and energy expenditure is higher, process stability is poor and there is the problem of potential safety hazard.
3, the precipitation conversion process of methyl maltol is all carried out in room temperature, the aqueous solution, not only eliminate because the distil degradation production of the methyl maltol caused of high temperature is brought in the process of sublimating and product in traditional partition method, affect product quality but also cause the problem of environmental pollution.
Embodiment
Embodiment 1
350mL water is added in 500mL there-necked flask, under agitation add 13.4g methyl maltol crude product (methyl maltol massfraction is 94.2%) and 9.4g hydrated barta, room temperature 26 DEG C difference stirring reaction 4,5,6,7 hours, by reaction mixture suction filtration, be washed to PH8, the oven dry of filter excess 105 DEG C, obtains white powder methyl maltol barium and is respectively 18.2g, 19.1g, 19.2g, 19.1g.Yield is respectively 93.8%, 98.5%, 99.0% and 98.5%.
Embodiment 2
350mL water is added in 500mL there-necked flask, under agitation add 13.4g methyl maltol crude product (methyl maltol massfraction is 94.2%) and 9.4g hydrated barta, room temperature 26 DEG C, 40 DEG C, 60 DEG C, 80 DEG C stirring reactions 5.5 hours is respectively in temperature of reaction, by reaction mixture suction filtration, be washed to PH8, the oven dry of filter excess 105 DEG C, obtains white powder methyl maltol barium and is respectively 19.2g, 19.1g, 18.9g, 18.7g.Yield is respectively 99.0%, 98.5%, 97.4% and 96.4%.
Embodiment 3
350mL water is added in 500mL there-necked flask, under agitation add 13.4g methyl maltol crude product (methyl maltol massfraction is 94.2%), add hydrated barta 8.6g (equimolar amount), 9.0g (excessive 5%), 9.4g (excessive 10%), 10.3g (excessive 20%) respectively, be room temperature 26 DEG C of stirring reactions 5.5 hours in temperature of reaction, by reaction mixture suction filtration, be washed to PH8, the oven dry of filter excess 105 DEG C, obtains white powder methyl maltol barium and is respectively 17.8g, 18.4g, 19.1g, 19.2g.Yield is respectively 91.8%, 95.8%, 98.5% and 99.0%.
Embodiment 4
350mL water is added in 500mL there-necked flask, under agitation add 13.4g methyl maltol crude product (methyl maltol massfraction is 94.2%) and 8.4g barium oxide (excessive 10%), room temperature 26 DEG C of stirring reactions 5.5 hours, by reaction mixture suction filtration, be washed to PH8, the oven dry of filter excess 105 DEG C, obtaining white powder methyl maltol barium is 19.1g, and yield is 98.5%.
Embodiment 5
350mL water is added in 500mL there-necked flask, under agitation add 13.4g methyl maltol crude product (methyl maltol massfraction is 94.2%) and 9.4g hydrated barta (excessive 10%), room temperature 26 DEG C of stirring reactions 5.5 hours, by reaction mixture suction filtration, be washed to PH8, the oven dry of filter excess 105 DEG C, has carried out 6 tests altogether according to the method for embodiment 5, the amount on average obtaining white powder methyl maltol barium is 19.2g, and yield is 99.0%.
Embodiment 6
According to the method for embodiment 4,5, change the solvent in embodiment into methyl alcohol respectively and ethanol is tested, the yield of methyl maltol barium is respectively 98.2% and 98.4%.According to the method according to embodiment 4,5, the consumption having carried out water is tested the impact of methyl maltol barium yield, and result shows, suitable solvent load is 300mL-500mL.
Embodiment 7
90mL water is added respectively in four 250mL there-necked flasks, sodium sulfate 7.3g (equimolar amount) is added respectively under stirring, 7.7g (excessive 5%), 8.1g (excessive 10%), 8.8g (excessive 20%) dissolves, add the methyl maltol barium 20g prepared according to embodiment 5 respectively, room temperature 26 DEG C of stirring reactions 3 hours, suction filtration, with 10mL water washing filter cake, merging filtrate and washings, obtain methyl maltol sodium solution, with sulfuric acid acidation to PH2-3, crystallization 4 hours under room temperature, through suction filtration, washing, dry, obtain white powder methyl maltol 11.0g, 11.2g, 11.4g, 11.5g, yield is 84.6%, 86.2%, 87.7%, 88.5%.Filter cake 105 DEG C oven dry, obtains white powder barium sulfate 11.7g, 11.9g, 12.0g, 12.0g, and yield is 97.3%, 98.9%, 99.8%, 99.8%.
Embodiment 8
90mL water is added respectively in four 250mL there-necked flasks, add sodium sulfate 8.1g (excessive 10%) under stirring to dissolve, add the methyl maltol barium 20g prepared according to embodiment 5, at room temperature 26 DEG C stirring reaction 2 respectively, 3, 4, 5 hours, suction filtration, with 10mL water washing filter cake, merging filtrate and washings, obtain methyl maltol sodium solution, with sulfuric acid acidation to PH2-3, crystallization 4 hours under room temperature, through suction filtration, washing, dry, obtain white powder methyl maltol 10.7g, 11.4g, 11.4g, 11.5g, yield is 82.3%, 87.7%, 87.7%, 88.5%.
Embodiment 9
90mL water is added respectively in four 250mL there-necked flasks, add sodium sulfate 8.1g (excessive 10%) under stirring to dissolve, add the methyl maltol barium 20g prepared according to embodiment 5, 26 DEG C are respectively in temperature, 40 DEG C, 60 DEG C, 80 DEG C of stirring reactions 3 hours, suction filtration, with 10mL water washing filter cake, merging filtrate and washings, obtain methyl maltol sodium solution, with sulfuric acid acidation to PH2-3, crystallization 4 hours under room temperature, through suction filtration, washing, dry, obtain white powder methyl maltol 11.4g, 11.3g, 11.4g, 11.5g, yield is 87.7%, 86.9%, 87.7%, 88.5%.
Embodiment 10
Add sodium sulfate 8.1g (excessive 10%) add 90mL water, stirring in 250mL there-necked flask under to dissolve, adding the methyl maltol barium 20g prepared according to embodiment 5, is 26 DEG C of stirring reactions 3 hours in temperature, suction filtration, with 10mL water washing filter cake, merging filtrate and washings, obtain methyl maltol sodium solution, with sulfuric acid acidation to PH2-3, crystallization 4 hours under room temperature, through suction filtration, washing, drying, obtain white powder methyl maltol 11.3g, yield is 86.9%.Filter cake 105 DEG C oven dry, obtains white powder barium sulfate 11.9g, and yield is 98.9%.
Embodiment 11
Methyl maltol crystalline mother solution about the 90mL obtained according to the method for embodiment 10 is added in 250mL there-necked flask, add sodium sulfate 0.15g under stirring to dissolve, add the methyl maltol barium 20g prepared according to embodiment 5, be 26 DEG C of stirring reactions 3 hours in temperature, suction filtration, with 10mL water washing filter cake, merging filtrate and washings, obtain methyl maltol sodium solution, with sulfuric acid acidation to PH2-3, crystallization 4 hours under room temperature, through suction filtration, washing, drying, obtain white powder methyl maltol 12.7g, yield is 97.7%.Carried out 9 crystalline mother solutions altogether according to the method for embodiment 11 and recycled test, methyl maltol average yield is 97.5%.
Embodiment 12
Methyl maltol prepared by the method according to embodiment 11 is joined in 60-70 DEG C of appropriate ethanol and dissolve, be cooled to 5 DEG C of recrystallizations, obtain methyl maltol finished product through centrifugation, washing, drying.Adopt high-efficient liquid phase chromatogram technique analysis, methyl maltol massfraction is 99.46%; The massfraction of the methyl maltol adopting Traditional Method to be separated is 99.22%.

Claims (3)

1. a separation method for methyl maltol, is characterized in that described separation method comprises the following steps:
1) at room temperature, methyl maltol crude product is added in solvent with hydrated barta or barium oxide and reacts, through suction filtration, washing, obtain methyl maltol barium;
2) methyl maltol barium step 1 obtained and sodium sulfate at room temperature, react in the aqueous solution, generate methyl maltol sodium and barium sulfate, obtain methyl maltol sodium solution and barium sulfate precipitate through centrifugation; Wherein barium sulfate is through washing, dry as byproduct;
3) methyl maltol sodium solution is through acidifying, crystallization, centrifugation, obtains methyl maltol and aqueous sodium persulfate solution, and methyl maltol obtains finished product through ethyl alcohol recrystallization, oven dry; Aqueous sodium persulfate solution then can be recycled.
2. the separation method of methyl maltol according to claim 1, the solvent that it is characterized in that in described step 1 is any one in water, methyl alcohol, ethanol.
3. the separation method of methyl maltol according to claim 1, is characterized in that described step 1,2 is all carried out in enamel reaction still.
CN201410545715.5A 2014-10-15 2014-10-15 A kind of separation method of methyl maltol Active CN104356102B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410545715.5A CN104356102B (en) 2014-10-15 2014-10-15 A kind of separation method of methyl maltol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410545715.5A CN104356102B (en) 2014-10-15 2014-10-15 A kind of separation method of methyl maltol

Publications (2)

Publication Number Publication Date
CN104356102A CN104356102A (en) 2015-02-18
CN104356102B true CN104356102B (en) 2016-02-17

Family

ID=52523439

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410545715.5A Active CN104356102B (en) 2014-10-15 2014-10-15 A kind of separation method of methyl maltol

Country Status (1)

Country Link
CN (1) CN104356102B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110903271A (en) * 2019-12-20 2020-03-24 安徽金禾实业股份有限公司 Method for recovering ethyl maltol in waste residue by acid-base neutralization method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5557582A (en) * 1978-10-23 1980-04-28 Meiji Seika Kaisha Ltd Purification of pyrone derivative
CN103113339B (en) * 2012-11-11 2015-03-11 安徽金禾实业股份有限公司 Maltol separation and purification method
CN103570658A (en) * 2013-11-01 2014-02-12 安徽金禾实业股份有限公司 Decolorizing and recrystallizing method of methyl maltol

Also Published As

Publication number Publication date
CN104356102A (en) 2015-02-18

Similar Documents

Publication Publication Date Title
CN106928055B (en) A method of aspirin is catalyzed and synthesized using choline eutectic solvent
CN104844412B (en) A kind of preparation method of 1,2,4-trifluoro-benzene
CN102395591B (en) Method for preparing prasugrel
CN104356102B (en) A kind of separation method of methyl maltol
CN104387291B (en) Preparation method of 1,3,6-hexanetricarbonitrile
CN107176906A (en) A kind of synthetic method of substitution indone
CN102993114B (en) A kind of production method of 1H-TETRAZOLE-5-acetic acid
CN103130708B (en) A kind of preparation method of N-tertbutyloxycarbonyl-4-nitro piperidines
CN102167716A (en) Synthesis method of clofarabine, midbody thereof and preparation method of midbody
CN103665084A (en) Method for preparing abiraterone acetate
CN103012288A (en) Preparation method of 6-chloro-1,3-dimethyluracil
CN104529935B (en) Method for synthesizing ethyl 2-(3-aldehyde-4-isobutyloxyphenyl)-4-methylthiazole-5-formate
CN104497048A (en) Preparation method of minodronic acid
CN103319548A (en) Purification method for cane sugar-6-acetate
CN104151170A (en) 4-nitrophenethylamine hydrochloride and preparation method thereof
CN105315197A (en) 2-chloro-5-pyridylaldehyde production method
CN105130972A (en) Emtricitabine benzoate, preparation method thereof, and method of preparing emtricitabine from emtricitabine benzoate
CN109608378A (en) A kind of preparation method of captopril isomers
CN107417622B (en) A refining method of 4(5) -chloro-2-cyano-5 (4) - (4' -methylphenyl) imidazole
CN108530380B (en) Synthesis method of N-methyl-1, 2-benzisothiazolin-3-one
CN103664758B (en) The synthetic method of Mexidole
CN103183599A (en) Method for preparing 2-valproic acid
CN105859548A (en) Method for catalyzed synthesis of 1,4-cyclohexanedicarboxylic acid
CN101787035A (en) Preparation method of 7-aminocephalo-5-mercapto-1-methyltetrazole
CN105294416A (en) 1,5-dicarbonyl derivative and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant