CN110407787A - A method of regulation chlorination-hydrolysis prepares maltol and its homologue - Google Patents
A method of regulation chlorination-hydrolysis prepares maltol and its homologue Download PDFInfo
- Publication number
- CN110407787A CN110407787A CN201910777306.0A CN201910777306A CN110407787A CN 110407787 A CN110407787 A CN 110407787A CN 201910777306 A CN201910777306 A CN 201910777306A CN 110407787 A CN110407787 A CN 110407787A
- Authority
- CN
- China
- Prior art keywords
- maltol
- homologue
- chlorination
- regulation
- reaction
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic 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
- C07D309/36—Heterocyclic 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
- C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a kind of methods that regulation chlorination-hydrolysis prepares maltol and its homologue, this method is by regulating and controlling chlorination reaction process, inhibit the polymerization reaction under α-furyl alkanol acid condition, improves the conversion ratio of main reaction, obtain the target product of high yield.Preparation method of the invention makes the methyl maltol of preparation and the yield of ethylmaltol be up to 80% or more, greatly reduces the generation of by-product.
Description
Technical field
The present invention relates to maltol and its homologue preparation technical fields, anti-more particularly to a kind of regulation chlorination-hydrolysis
The method that maltol and its homologue should be prepared.
Background technique
Methyl maltol and ethylmaltol often make an addition to as foodstuff flavouring agent bakes food, in ice cream and candy,
Wherein for about 110 μ g/kg. of the additive amount of maltol according to calculating, the average daily intake of methyl maltol and ethylmaltol is 5
~29mg, but in certain crowds, actual consumption level may be several times of this average magnitude.
The preparation method of methyl maltol and ethylmaltol is the chlorine using α-furyl alkanol and 2 times of molecular weight at present
In methanol aqueous solution after the reaction was completed, then heated hydrolysis obtains maltol and its homologue.I.e. equipped with Dropping feeder and
In the reaction unit of logical chlorine, a certain amount of methanol aqueous solution is added as solvent, at a certain temperature, α-furyl alkanol and
Chlorine is passed into reaction unit and is reacted in certain proportion (molar ratio 1:2.05~2.1), and it is chloro- to obtain 2- alkyl -4-
The oligomer of 6- hydroxyl -1,3- pyrone compound and by-product α-furyl alkanol, after being added dropwise to complete to reaction mixture into
Row heat temperature raising, chloro- 6- hydroxyl -1, the 3- pyranone hydrolysis of 2- alkyl -4-, which is reset, generates -3 hydroxyls of 2- alkyl-Isosorbide-5-Nitrae-pyranone
Compound is that is, maltol and its homologue；The oligomer of α-furyl alkanol occurs acutely poly- under the action of strong acid high temperature simultaneously
Close the black by-products of tar that reaction generates resinoid class.Reaction process square formula:
This method is to prepare the main stream approach of methyl maltol and ethylmaltol at present, at present domestic manufacturer all be
This method.The reaction has the disadvantage that the yield of maltol homologue is lower, about 60% or so, generate a large amount of resinae
Black by-products of tar 40% or so.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of regulation chlorination-hydrolysis to prepare maltol and its homologue
Method.The present invention inhibits the polymerization reaction under α-furyl alkanol acid condition by regulation chlorination reaction process, improves main anti-
The conversion ratio answered obtains the target product of high yield.
Technical solution of the present invention the following steps are included:
1) in a solvent in molar ratio it is that 1:1 is sufficiently reacted with chlorine by α-furyl alkanol, generates unstable 2,
4- dichloro--α-dihydrofuran alkanol compounds；
2) alcoholic solution is added in the system after step 1) reaction, and placing it in temperature is 0-10 DEG C, reacts 30min-
60min generates 6- hydroxyl -2- alkyl -1,3- pyrone compound；
3) system after step 2) reaction is then cooled to 0 DEG C hereinafter, being slowly introducing again into reaction system and step
1) chlorine of α-furyl alkanol equimolar amounts in generates chloro- 6- hydroxyl -1, the 3- pyranone compounds of 2- alkyl -4-；
4) system after step 3) reaction is to slowly warm up to 50-70 DEG C, alcoholic solution is then added, reaction is hydrolyzed, obtains
To maltol and its homologue.
Preferably, the maltol and its homologue are respectively methyl maltol and ethylmaltol.
Preferably, solvent described in step 1) is one or both of carbon tetrachloride or chloro silicone oil.
Preferably, step 2) and alcoholic solution described in step 4) are ethanol water or methanol aqueous solution.
It is further preferred that ethyl alcohol or methanol concentration 50-80% in the ethanol water or methanol aqueous solution.
Particularly preferred, the additional amount of alcoholic solution accounts for the 50-60% of liquor capacity in reaction system in the step 2).
Particularly preferred, the additional amount of alcoholic solution accounts for the 20-30% of liquor capacity in reaction system in the step 4).
Compared with prior art, the invention has the following advantages:, the target product that technical solution of the present invention obtains
The yield of (methyl maltol and ethylmaltol) is increased to 80% or more, and by-product, that is, resinae tar of generation is reduced to
20% or less；
Chlorination reaction temperature easily controls in preparation process of the invention, and reaction temperature can be reacted at 0 DEG C or so,
Yield is not influenced, production cost is greatly reduced.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without any creative labor, can also be according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the chemical reaction mechanism figure that the present invention prepares maltol and its homologue.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
A kind of preparation method of methyl maltol, comprising the following steps:
1) 1mol α-furyl methane alcohol is placed in 100mL carbon tetrachloride, then passes to 1mol chlorine and is sufficiently reacted
2h generates unstable 2,4- dichloro--α-dihydrofuran alkanol compounds；
2) 55mL ethanol content is added in the system after step 1) reaction and is 70% ethanol water, and place it in
Temperature is 8 DEG C, reacts 50min, generates 6- hydroxyl -2- alkyl -1,3- pyrone compound；
3) system after step 2) reaction is then cooled to 0 DEG C hereinafter, being slowly introducing again into reaction system and 1mol
Chlorine generates chloro- 6- hydroxyl -1, the 3- pyranone compounds of 2- alkyl -4-；
4) system after step 3) reaction is to slowly warm up to 60 DEG C, the ethyl alcohol that 25mL ethanol content is 50% is then added
Reaction is hydrolyzed in aqueous solution, obtains methyl maltol.
Embodiment 2
A kind of preparation method of ethylmaltol, comprising the following steps:
1) 1mol α-furyl ethane alcohol is placed in 100mL carbon tetrachloride, then passes to 1mol chlorine and is sufficiently reacted
2h generates unstable 2,4- dichloro--α-dihydrofuran alkanol compounds；
2) 55mL ethanol content is added in the system after step 1) reaction and is 70% ethanol water, and place it in
Temperature is 10 DEG C, reacts 60min, generates 6- hydroxyl -2- alkyl -1,3- pyrone compound；
3) system after step 2) reaction is then cooled to 0 DEG C hereinafter, being slowly introducing again into reaction system and 1mol
Chlorine generates chloro- 6- hydroxyl -1, the 3- pyranone compounds of 2- alkyl -4-；
4) system after step 3) reaction is to slowly warm up to 58 DEG C, the ethyl alcohol that 25mL ethanol content is 50% is then added
Reaction is hydrolyzed in aqueous solution, obtains ethylmaltol.
Through detecting, the yield of the methyl maltol and ethylmaltol that prepare in Example 1 and Example 2 of the present invention exists
80% or more.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention；At the same time, for those skilled in the art, foundation
Thought of the invention, there will be changes in the specific implementation manner and application range.In conclusion the content of the present specification is not
It is interpreted as limitation of the present invention.
Claims (7)
1. a kind of method that regulation chlorination-hydrolysis prepares maltol and its homologue, which is characterized in that including following step
It is rapid:
1) in a solvent in molar ratio it is that 1:1 is sufficiently reacted with chlorine by α-furyl alkanol, generates unstable 2,4- bis-
Chloro-α-dihydrofuran alkanol compounds；
2) alcoholic solution is added in the system after step 1) reaction, and placing it in temperature is 0-10 DEG C, reacts 30min-
60min generates 6- hydroxyl -2- alkyl -1,3- pyrone compound；
3) then by step 2) reaction after system be cooled to 0 DEG C hereinafter, be slowly introducing again into reaction system in step 1)
The chlorine of α-furyl alkanol equimolar amounts generates chloro- 6- hydroxyl -1, the 3- pyranone compounds of 2- alkyl -4-；
4) system after step 3) reaction is to slowly warm up to 50-70 DEG C, alcoholic solution is then added, reaction is hydrolyzed, obtains wheat
Bud phenol and its homologue.
2. regulation chlorination-hydrolysis according to claim 1 prepares the method method of maltol and its homologue, special
Sign is that the maltol and its homologue are respectively methyl maltol and ethylmaltol.
3. the method that regulation chlorination-hydrolysis according to claim 1 prepares maltol and its homologue, feature exist
In solvent described in step 1) is one or both of carbon tetrachloride or chloro silicone oil.
4. the method that regulation chlorination-hydrolysis according to claim 1 prepares maltol and its homologue, feature exist
In alcoholic solution described in step 2) and step 4) is ethanol water or methanol aqueous solution.
5. the method that regulation chlorination-hydrolysis according to claim 4 prepares maltol and its homologue, feature exist
In ethyl alcohol or methanol concentration in the ethanol water or methanol aqueous solution are 50-80%.
6. the method that regulation chlorination-hydrolysis according to claim 5 prepares maltol and its homologue, feature exist
In the additional amount of alcoholic solution accounts for the 50-60% of liquor capacity in reaction system in the step 2).
7. the method that regulation chlorination-hydrolysis according to claim 5 prepares maltol and its homologue, feature exist
In the additional amount of alcoholic solution accounts for the 20-30% of liquor capacity in reaction system in the step 4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910777306.0A CN110407787B (en) | 2019-08-22 | 2019-08-22 | Method for preparing maltol and homologues thereof by regulating chlorination-hydrolysis reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910777306.0A CN110407787B (en) | 2019-08-22 | 2019-08-22 | Method for preparing maltol and homologues thereof by regulating chlorination-hydrolysis reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110407787A true CN110407787A (en) | 2019-11-05 |
| CN110407787B CN110407787B (en) | 2021-11-30 |
Family
ID=68368456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910777306.0A Active CN110407787B (en) | 2019-08-22 | 2019-08-22 | Method for preparing maltol and homologues thereof by regulating chlorination-hydrolysis reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110407787B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115716814A (en) * | 2022-11-18 | 2023-02-28 | 上海万香日化有限公司 | Synthesis method of 2-tert-butyl-3-hydroxy-4-pyrone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947950A (en) * | 2018-07-27 | 2018-12-07 | 重庆华控康乐药物研究有限公司 | A kind of preparation method of native malt phenol |
-
2019
- 2019-08-22 CN CN201910777306.0A patent/CN110407787B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947950A (en) * | 2018-07-27 | 2018-12-07 | 重庆华控康乐药物研究有限公司 | A kind of preparation method of native malt phenol |
Non-Patent Citations (1)
| Title |
|---|
| T.M. BRENNAN ET AL.,: "A NOVEL SYNTHESIS OF MALTOL AND RELATED γ-PYRONES", 《TETRAHEDRON LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115716814A (en) * | 2022-11-18 | 2023-02-28 | 上海万香日化有限公司 | Synthesis method of 2-tert-butyl-3-hydroxy-4-pyrone |
| CN115716814B (en) * | 2022-11-18 | 2024-08-30 | 上海万香日化有限公司 | Synthesis method of 2-tert-butyl-3-hydroxy-4-pyrone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110407787B (en) | 2021-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106008295B (en) | A kind of preparation method of the alkylthio group toluene of 2 halo 6 | |
| CN110407787A (en) | A method of regulation chlorination-hydrolysis prepares maltol and its homologue | |
| CN100362009C (en) | 2-deoxidized glucose preparation method | |
| CN109020849A (en) | A kind of preparation method of deuterated dimethyl sulfoxide | |
| CN103058984B (en) | Synthesis method of watermelon ketone | |
| CN107473948A (en) | A kind of synthetic method that the pentanone of 3,5 dichloro 2 is prepared by ethyl acetoacetate | |
| CN111018706A (en) | Synthesis method of 4, 4' -diphenyl ether dicarboxylic acid | |
| CN108569948A (en) | A kind of preparation method of the chloro- 4- toluene fluorides of 2- | |
| CN107513012A (en) | A kind of continuous method for preparing 1 (4 chlorphenyl) 1 butanone | |
| CN107814686B (en) | A kind of preparation method of deuterated chloroform | |
| CN107501171B (en) | Synthetic method of 2-chloro-3-pyridylaldehyde | |
| CN104478715B (en) | The preparation method of compound | |
| CN105017363B (en) | 3-ketone-4-androstene-17 β carboxylic acid and the synthetic method of methyl ester thereof | |
| CN105237340B (en) | Novel synthesis method for 4,4,4-trifluorobutanol | |
| CN110437092A (en) | A kind of preparation method of ticagrelor key intermediate aromatic cyclopropane amide | |
| CN110003167A (en) | A kind of synthetic method of 2- thiophene acetic acid | |
| CN103980108A (en) | Method for preparing 2-(1-methylalkyl) succinic acid | |
| CN103232344A (en) | Method for synthesizing S-2-methyl chloropropionate | |
| CN104418778A (en) | Practical synthetic method for clethodim intermediate | |
| CN101565369B (en) | Method for preparing 3-bromine-5-trifluoromethylbenzoic acid | |
| CN109574845A (en) | The preparation method of the chloro- 4,4,4- trifluoroacetic ethyl acetoacetate of 2- | |
| CN102285878B (en) | Method for preparing 2-halo-4,5-dimethoxy benzoic acid | |
| CN107935858A (en) | The preparation method of 5 fluorine, 2 nitrophenol | |
| JPH0717899A (en) | Production of carboxylic acid chloride | |
| US11970507B2 (en) | Method for preparing 2-arylmalonic acid derivative and intermediate, and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |