CN108947950A - A kind of preparation method of native malt phenol - Google Patents
A kind of preparation method of native malt phenol Download PDFInfo
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- CN108947950A CN108947950A CN201810840679.3A CN201810840679A CN108947950A CN 108947950 A CN108947950 A CN 108947950A CN 201810840679 A CN201810840679 A CN 201810840679A CN 108947950 A CN108947950 A CN 108947950A
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of native malt phenol preparation methods.This method is native malt phenol preparation method, has and avoids making and using methyl-metals halide, directly restores the features such as 2- furans ethyl alcohol is made with natural 2- acetyl furan.Method and process of the invention is simple, and occupancy equipment is few, easy to operate, avoids methyl halide to air pollution and to the occupational hazards of operator, is suitable for industrialized production.
Description
Technical field
The invention belongs to fragrance and pharmaceutical chemistry technical field, and in particular to a kind of preparation method of native malt phenol.
Background technique
Native malt phenol, English name: Maltene, chemical name: 3- hydroxy-2-methyl-pyrokomane, CAS:118-71-
8, chemical structural formula is as follows:
Maltol is naturally present in and the plants such as witloof, larch, needle pine bark in.Maltol is a kind of burnt odor type
Fragrance synergist is widely used in food, beverage, candy, drinks, is the second largest food for being only second to vanillic aldehyde in tobacco essence
With fragrance kind；Maltol is also used for pharmaceutic adjuvant, and " Chinese Pharmacopoeia " (2015 editions) are recorded.
Industrially common native malt phenol is mostly, using natural furfural as raw material, first to prepare methyl halide with natural methanol at present
Compound and magnesium metal carry out grignard reaction and methyl-magnesium-halide are made, and 2- furans is made carrying out grignard coupling reaction with natural furfural
Then ethyl alcohol is reset to obtain maltol by chlorinated hydrolysis, reaction equation is as follows:
Maltol obtained by said synthesis route, the equipment investment for needing to prepare Methochloride is big, comprehensive energy consumption is high,
The three wastes are big to human body and environmental hazard, it is also necessary to carry out the grignard reaction of anhydrous and oxygen-free, reaction condition is more harsh；Solvent is common
The toxicity such as ether, tetrahydrofuran, 2- methyltetrahydrofuran are higher, easily form explosive peroxide object, while price is more expensive, is unfavorable for
Recycling；Raw material monochloro methane, a bromomethane itself are more toxic；One bromomethane environmental pollution is serious, especially to ozone layer
Consumption is serious.
The natural product of 2- acetyl furan are present in the volatility of coffee, tomato, beer, green tea, raisins and potato block
Fragrant ingredient etc..Edible alcohol is " national food safety standard edible alcohol " (GB31640-2016)
Summary of the invention
Technical problem to be solved by the present invention lies in a kind of preparation methods of native malt phenol, solve industrial producer
The universal material toxicity of method is big, environmental pollution is serious, production efficiency of equipment is low, the reaction time is long, wastewater flow rate is big, organic residual solvent
The defects of high, the native malt phenol that this method obtains reach the requirement of " Chinese Pharmacopoeia " (version in 2015).
1. a kind of preparation method of native malt phenol, which comprises the following steps:
1) it is restored by natural 2- acetyl furan (formula III), under reducing agent effect, obtains 2- furans ethyl alcohol (Formula II), react
Formula is as follows,
2) 2- furans ethyl alcohol (Formula II) is passed through in the aqueous solution containing natural methanol to chlorine and carries out oxidation reaction, then
Native malt phenol crude product (Formulas I) is reset to obtain in acid-catalyzed hydrolysis, reaction equation is as follows,
3) after native malt phenol crude product (Formulas I) to be dissolved to decoloration in edible alcohol, maltol finished product is recrystallized to obtain.
2. according to the method described in claim 1, it is characterized in that the reducing agent in the step is palladium/charcoal.
3. according to the method described in claim 2, it is characterized in that reducing agent palladium/charcoal in the step be 5% palladium/
Charcoal, 10% palladium/charcoal.
4. according to method described in claim 1, it is characterised in that: the reaction of the step 1) is using itself as solvent.
5. according to method described in claim 1, it is characterised in that: the catalyst for hydrogenation mass ratio of the step 1) is
2- acetyl furan: catalyst=1: (0.01~0.1), preferably 1: 0.02.
6. according to method described in claim 1, it is characterised in that: reduction reaction temperature in the step 1) is 40 DEG C~
120℃。
7. according to method described in claim 1, it is characterised in that: 3 hours reduction reaction time in the step 1)~
16 hours.
8. according to method described in claim 1, it is characterised in that: the reduction reaction pressure in the step 1) is 0.2MPa
~2.0MPa, preferably 1.1MPa~1.3MPa.
Advantages of the present invention is as follows:
1, the high income of the resulting native malt phenol of preparation method of the invention, total recovery may be up to 80%, and quality reaches
" Chinese Pharmacopoeia " (version in 2015) pharmaceutic adjuvant standard, the addition of " national food safety standard " (GB1886-282-2016) food
Agent and " U.S.'s food chemicals code " (FCC-9) standard.
2, the preparation method production of native malt phenol of the invention, equipment capacity can be improved 2~3 times, improve yield,
And energy conservation, consumption reduction, reduce production cost.
3, short when the preparation method of the invention is reacted compared with method in the prior art, the impurity of generation is few.
4, the preparation method of the invention has that operation is simpler, low energy consumption, wastewater flow rate is few, has compared with method in the prior art
The advantages that machine residual solvent is few.
5, methyl halide is reduced in the preparation method of the invention and ether solvent is few to the harm of environment and human body, it can industry
Change large-scale production.
6, primary raw material 2- acetyl furan used in the present invention, chlorine, methanol and water are cheap and be easy to get, although
Catalyst palladium carbon is more expensive, but can continuously apply, and producer's recycling activation, overall cost are low.
It is further illustrated by embodiment and explains native malt phenol preparation method of the present invention, but do not limit model of the invention
It encloses.Wherein temperature be degree Celsius, yield be by the molar yield calculated 2- acetyl furan.
Specific embodiment
Embodiment 1
2- acetyl furan 220.0g is added in the autoclave of clean dried, 10% palladium charcoal butt 4.5g, nitrogen is added
After displacement, add hydrogen to pressure 0.5MPa, after reaction 0.5 hour, control temperature 50 C~55 DEG C, maintenance pressure 1.1MPa~
1.3MPa reacts 8 hours, palladium charcoal is recovered by filtration and directly applies lower batch, filtrate is spare.
Methanol 700.0g, water 400.0g are added in clean reaction flask, -20 DEG C~-15 DEG C are cooled in stirring, in dropwise addition
The mixed liquor of step preparation filtrate and methanol 220.0g, while being passed through chlorine and carrying out oxychloride reaction, exothermic heat of reaction, speed is added dropwise in control
Degree and logical chlorine speed, make reaction temperature be maintained at -20 DEG C~-15 DEG C, and about 5~6h is added dropwise, and are further continued for logical chlorine 30min, always
Reaction was completed when logical chlorine dose 320g.Residual chlorine is recovered under reduced pressure, then methanol is recycled in air-distillation, until interior temperature reaches 100 DEG C,
It is changed to back hydrolysis reaction 2-3h, is cooled to 20 DEG C~30 DEG C, stirring is lower to use 30% sodium hydrate aqueous solution, adjusting pH to 2~
3, -5 DEG C are then refrigerated to, is precipitated maltol crystal crude product 297.5g (moisture 25%).The crude product dissolves by edible alcohol, is de-
After the technical process such as color, crystallization, filtration washing, drying, maltol finished product 201.6g, yield 80.0%, content 99.5% are obtained.
Embodiment 2
2- acetyl furan 110.0g is added in the autoclave of clean dried, 5% palladium charcoal butt 5.5g is added, nitrogen is set
After changing, add hydrogen to pressure 0.5MPa, after reaction 0.5 hour, control temperature 50 C~55 DEG C, maintenance pressure 1.3MPa~
1.6MPa reacts 7 hours, palladium charcoal is recovered by filtration and directly applies lower batch, filtrate is spare.
Methanol 350.0g, water 200.0g are added in clean reaction flask, -20 DEG C~-15 DEG C are cooled in stirring, in dropwise addition
The mixed liquor of step preparation filtrate and methanol 220.0g, while being passed through chlorine and carrying out oxychloride reaction, exothermic heat of reaction, speed is added dropwise in control
Degree and logical chlorine speed, make reaction temperature be maintained at -20 DEG C~-15 DEG C, and about 5~6h is added dropwise, and are further continued for logical chlorine 30min, always
Reaction was completed when logical chlorine dose 160g.Residual chlorine is recovered under reduced pressure, then methanol is recycled in air-distillation, until interior temperature reaches 100 DEG C,
It is changed to back hydrolysis reaction 2-3h, is cooled to 20 DEG C~30 DEG C, stirring is lower to use 30% sodium hydrate aqueous solution, adjusting pH to 2~
3, -5 DEG C are then refrigerated to, is precipitated maltol crystal crude product 149.2g (moisture 26%).The crude product dissolves by edible alcohol, is de-
After the technical process such as color, crystallization, filtration washing, drying, maltol finished product 101.5g, yield 80.5%, content 99.6% are obtained.
Embodiment 3
2- acetyl furan 110.0g, methanol 220.0g is added in the autoclave of clean dried, 5% palladium charcoal butt is added
5.5g after nitrogen displacement, adds hydrogen to control temperature 50 C~55 DEG C after reaction 0.5 hour to pressure 0.5MPa, maintains pressure
1.3MPa~1.6MPa reacts 7 hours, palladium charcoal is recovered by filtration and directly applies lower batch, filtrate is spare.
Methanol 220.0g, water 200.0g are added in clean reaction flask, -20 DEG C~-15 DEG C are cooled in stirring, in dropwise addition
The mixed liquor of step preparation filtrate and methanol 220.0g, while being passed through chlorine and carrying out oxychloride reaction, exothermic heat of reaction, speed is added dropwise in control
Degree and logical chlorine speed, make reaction temperature be maintained at -20 DEG C~-15 DEG C, and about 5~6h is added dropwise, and are further continued for logical chlorine 30min, always
Reaction was completed when logical chlorine dose 160g.Residual chlorine is recovered under reduced pressure, then methanol is recycled in air-distillation, until interior temperature reaches 100 DEG C,
It is changed to back hydrolysis reaction 2h~3h, is cooled to 20 DEG C~30 DEG C, lower 30% sodium hydrate aqueous solution of stirring adjusts pH to 2
~3, -5 DEG C are then refrigerated to, is precipitated maltol crystal crude product 152.2g (moisture 28%).The crude product by edible alcohol dissolution,
After the technical process such as decoloration, crystallization, filtration washing, drying, maltol finished product 98.1g, yield 77.9%, content are obtained
99.5%.
Embodiment 4
2- acetyl furan 110.0g is added in the autoclave of clean dried, 5% palladium charcoal butt 5.5g is added, nitrogen is set
After changing, add hydrogen to pressure 0.5MPa, after reaction 0.5 hour, 40 DEG C~45 DEG C of temperature of control, maintenance pressure 1.3MPa~
1.6MPa reacts 12 hours, palladium charcoal is recovered by filtration and directly applies lower batch, filtrate is spare.
Methanol 350.0g, water 200.0g are added in clean reaction flask, -20 DEG C~-15 DEG C are cooled in stirring, in dropwise addition
The mixed liquor of step preparation filtrate and methanol 220.0g, while being passed through chlorine and carrying out oxychloride reaction, exothermic heat of reaction, speed is added dropwise in control
Degree and logical chlorine speed, make reaction temperature be maintained at -20 DEG C~-15 DEG C, and about 5~6h is added dropwise, and are further continued for logical chlorine 30min, always
Reaction was completed when logical chlorine dose 160g.Residual chlorine is recovered under reduced pressure, then methanol is recycled in air-distillation, until interior temperature reaches 100 DEG C,
It is changed to back hydrolysis reaction 2-3h, is cooled to 20 DEG C~30 DEG C, stirring is lower to use 30% sodium hydrate aqueous solution, adjusting pH to 2~
3, -5 DEG C are then refrigerated to, is precipitated maltol crystal crude product 147.1g (moisture 25%).The crude product dissolves by edible alcohol, is de-
After the technical process such as color, crystallization, filtration washing, drying, maltol finished product 99.7g, yield 79.1%, content 99.4% are obtained.
Front has detailed the present invention, including its preferred embodiment.It is to be understood that in view of the present invention is public
The content opened, those skilled in the art can be changed and/or change to the present invention in the scope of described claims
Into these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of native malt phenol, which comprises the following steps:
1) it is restored by natural 2- acetyl furan (formula III), under reducing agent effect, obtains 2- furans ethyl alcohol (Formula II), reaction equation is such as
Under,
2) 2- furans ethyl alcohol (Formula II) is passed through in the aqueous solution containing natural methanol to chlorine and carries out oxidation reaction, then in acid
Catalyzing hydrolysis resets to obtain native malt phenol crude product (Formulas I), and reaction equation is as follows,
3) after native malt phenol crude product (Formulas I) to be dissolved to decoloration in edible alcohol, native malt phenol finished product is recrystallized to obtain.
2. according to the method described in claim 1, it is characterized in that the reducing agent in the step is palladium/charcoal.
3. according to the method described in claim 2, it is characterized in that reducing agent palladium/charcoal in the step be 5% palladium/charcoal,
10% palladium/charcoal.
4. according to method described in claim 1, it is characterised in that: the reaction of the step 1) is using itself as solvent.
5. according to method described in claim 1, it is characterised in that: the catalyst for hydrogenation mass ratio of the step 1) is 2- second
Acyl furans: catalyst=1: (0.01~0.1), preferably 1: 0.02.
6. according to method described in claim 1, it is characterised in that: the reduction reaction temperature in the step 1) is 40 DEG C~120
℃。
7. according to method described in claim 1, it is characterised in that: the reduction reaction time in the step 1) is 3 hours~16
Hour.
8. according to method described in claim 1, it is characterised in that: reduction reaction pressure in the step 1) be 0.2MPa~
2.0MPa, preferably 1.1MPa~1.3MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407787A (en) * | 2019-08-22 | 2019-11-05 | 河北省天利海香精香料有限公司 | A method of regulation chlorination-hydrolysis prepares maltol and its homologue |
Citations (3)
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| CN1142821A (en) * | 1994-01-31 | 1997-02-12 | 辉瑞大药厂 | Method of synthesizing gamma pyrones |
| CN106366061A (en) * | 2016-08-30 | 2017-02-01 | 安徽金禾实业股份有限公司 | Maltol pipe chlorination reaction method |
| CN107089962A (en) * | 2017-04-18 | 2017-08-25 | 山东新和成药业有限公司 | A kind of method that maltol and homologue are prepared by molecular oxygen oxidation |
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2018
- 2018-07-27 CN CN201810840679.3A patent/CN108947950A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142821A (en) * | 1994-01-31 | 1997-02-12 | 辉瑞大药厂 | Method of synthesizing gamma pyrones |
| CN106366061A (en) * | 2016-08-30 | 2017-02-01 | 安徽金禾实业股份有限公司 | Maltol pipe chlorination reaction method |
| CN107089962A (en) * | 2017-04-18 | 2017-08-25 | 山东新和成药业有限公司 | A kind of method that maltol and homologue are prepared by molecular oxygen oxidation |
Non-Patent Citations (2)
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| THOMAS C. MALIG，等: "Real-time HPLC-MS reaction progress monitoring using an automated analytical platform", 《REACTION CHEMISTRY & ENGINEERING》 * |
| THOMAS C. MALIG，等: "Supporting Information Real-time HPLC-MS reaction progress monitoring using an automated analytical platform", 《REACTION CHEMISTRY & ENGINEERING》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407787A (en) * | 2019-08-22 | 2019-11-05 | 河北省天利海香精香料有限公司 | A method of regulation chlorination-hydrolysis prepares maltol and its homologue |
| CN110407787B (en) * | 2019-08-22 | 2021-11-30 | 河北省天利海香精香料有限公司 | Method for preparing maltol and homologues thereof by regulating chlorination-hydrolysis reaction |
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Application publication date: 20181207 |