CN101597764A - A kind of electrolytic oxidation prepares 2-methyl-2,5-dimethoxy-2, the method for 5-dihydrofuran - Google Patents
A kind of electrolytic oxidation prepares 2-methyl-2,5-dimethoxy-2, the method for 5-dihydrofuran Download PDFInfo
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- CN101597764A CN101597764A CNA2009101575414A CN200910157541A CN101597764A CN 101597764 A CN101597764 A CN 101597764A CN A2009101575414 A CNA2009101575414 A CN A2009101575414A CN 200910157541 A CN200910157541 A CN 200910157541A CN 101597764 A CN101597764 A CN 101597764A
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Abstract
The invention provides and a kind ofly prepare 2-methyl-2 by 2-methyl furan electrolytic oxidation in methanol solution, 5-dimethoxy-2, the method for 5-dihydrofuran.This method steps: ionogen, 2-methyl furan and methyl alcohol are added in the electrolyzer, stir, energising reaction certain hour under constant current conditions.Reaction mixture concentrates and removes methyl alcohol, and the residuum underpressure distillation promptly gets product.
Description
The present invention relates to a kind of high-level efficiency, low cost and oligosaprobic preparation 2-methyl-2,5-dimethoxy-2, the method for 5-dihydrofuran.2-methyl-2,5-dimethoxy-2,5-dihydrofuran are the key intermediates of important meat perfume compound 2-methyl-3-furanthiol, and method of the present invention is significant for the green production that realizes 2-methyl-3-furanthiol.
In the operational path of traditional 2-methyl-3-furanthiol, 2-methyl-2,5-dimethoxy-2, the 5-dihydrofuran by the 2-methyl furan in the solution of methyl alcohol with bromine (or chlorine) prepared in reaction.This method need be used a large amount of liquid bromines or chlorine, and operation is very inconvenient, and cryogenic reaction conditions energy consumption is big.This method need be used stoichiometric alkali, produces a large amount of solid waste inorganic salt, and environment is caused great pollution.
Along with the growing interest of people to environmental problem, Green Chemistry becomes the main flow direction of current chemical developer, and eco-friendly friendly process becomes pursuing one's goal of numerous chemical enterprises, and organic electrosynthesis is one of development in recent years new synthetic technology of getting up.Organic electrosynthesis is the organic oxidation reduction process that is caused by the transfer transport between electrode and response matrix, be applicable to the fine chemical product that industrial scale is relatively little, added value is high, as spices, medicine, dyestuff, agricultural chemicals etc., now become one of important means of development fine chemistry industry.Because the Oxidizing and Reducing Agents in the chemosynthesis has been replaced in organic electrosynthesis method electricity consumption filial generation, building-up reactions can be carried out under the condition of low temperature, normal pressure, catalyst-free, technical process is short, selectivity of product is high, pollutes for a short time even pollution-free, and the title of " green industry " is arranged.
The objective of the invention is to utilize organic electrosynthesis technology, provide a kind of and prepare 2-methyl-2 by electrolytic oxidation, 5-dimethoxy-2, the green method of 5-dihydrofuran substitutes the traditional methodology of organic synthesis in 2-methyl-present operational path of 3-furanthiol.It is characterized in that in the electrolyzer of electrode is housed the oxidation of at room temperature switching on of the methanol solution of 2-methyl furan obtains 2-methyl-2,5-dimethoxy-2,5-dihydrofuran.Reaction formula is as follows:
The present invention relates to the 2-methyl-2 of formula (I), 5-dimethoxy-2, the preparation method of 5-dihydrofuran:
(I) 2-methyl-2,5-dimethoxy-2,5-dihydrofuran
Preparation method of the present invention, easy and simple to handle.Its main process is: a certain amount of ionogen, 2-methyl furan and methyl alcohol are added in the electrolyzer, are stirred to dissolving fully.With the tap water cool electrolysis cells that circulates, energising reaction certain hour under constant current conditions.Follow the tracks of reaction by GC, treat the completely dissolve of raw material 2-methyl furan after, reaction mixture concentrates and removes methyl alcohol, the cut of 95-97 ℃/9000Pa is collected in the residuum underpressure distillation.2-methyl-2,5-dimethoxy-2,5-dihydrofuran productive rate 70～80%.The methyl alcohol that distills out can recycle.
In the method for the present invention, do not need to use special electrolyzer, use the electrolyzer of single chamber to get final product.The ionogen that is used to improve the reaction solution electric conductivity can be various salt, as sodium-chlor, Repone K, Sodium Bromide, Potassium Bromide, yellow soda ash, salt of wormwood, sodium-acetate, Potassium ethanoate, benzene sulfonic acid sodium salt, Phenylsulfonic acid potassium etc., also can be alkali such as sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate etc.Generally electrolytic solution is composed as follows: 5 to 65%2-methyl furans, 1 to, 10% salt, 25 to, 94% methyl alcohol.Used anode is a material stable under electrolytic condition, comprises platinum, graphite or is coated with titanium of ru oxide etc., metal platinum and graphite better effects if.Cathode material can be iron, graphite or alloy.The used current density of electrolysis can be at 100～2500A/m
2Scope in change 200～1600A/m
2It is preferable scope.Electrolysis can be carried out under 0～60 ℃.
The present invention prepares 2-methyl-2 by electrolytic oxidation, 5-dimethoxy-2, and the method for 5-dihydrofuran will obtain concrete description by the following examples.
Embodiment 1
2g NaBr, 120mL methyl alcohol and 16.4g (0.2mol) 2-methyl furan are added in the electrolyzer that has chuck, are stirred to dissolving fully.Installing electrodes, anode and cathode material are graphite, and the electrode bottom is apart from the about 0.8cm of bottom of electrolytic tank.Constant current carries out electrolytic reaction, current density 800A/m at 0.9A
2Tap water circulation cool electrolysis cells, control reaction temperature is at 15-17 ℃.GC follows the tracks of reaction, raw material completely dissolve behind about 10h.The light brown mixture rotary evaporation of gained is removed methyl alcohol, and resistates filters, underpressure distillation, the cut of 95-97 ℃/9000Pa of collection, productive rate about 76%.
Embodiment 2
5g KBr, 150mL methyl alcohol and 20.5g (0.25mol) 2-methyl furan are added in the electrolyzer that has chuck, are stirred to dissolving fully.Installing electrodes, anode material are graphite, and cathode material is a stainless steel, and the electrode bottom is apart from the about 0.8cm of bottom of electrolytic tank.Constant current carries out electrolytic reaction, current density 500A/m at 0.6A
2Tap water circulation cool electrolysis cells, control reaction temperature is at 15-17 ℃.GC follows the tracks of reaction, raw material completely dissolve behind about 12h.The light brown mixture rotary evaporation of gained is removed methyl alcohol, and resistates filters, underpressure distillation, the cut of 95-97 ℃/9000Pa of collection, productive rate about 76%.
Embodiment 3
8g KOAc, 200mL methyl alcohol and 34.6g (0.3mol) 2-methyl furan are added in the electrolyzer that has chuck, are stirred to dissolving fully.Installing electrodes, anode and cathode material are graphite, and the electrode bottom is apart from the about 0.8cm of bottom of electrolytic tank.Constant current carries out electrolytic reaction, current density 500A/m at 0.5A
2Tap water circulation cool electrolysis cells, control reaction temperature is at 15-17 ℃.GC follows the tracks of reaction, raw material completely dissolve behind about 14h.The light brown mixture rotary evaporation of gained is removed methyl alcohol, and resistates filters, underpressure distillation, the cut of 95-97 ℃/9000Pa of collection, productive rate about 72%.
Embodiment 4
2g NaBr, 100mL methyl alcohol and 16.4g (0.2mol) 2-methyl furan are added in the electrolyzer that has chuck, are stirred to dissolving fully.Installing electrodes, anode are platinum electrode, and negative electrode is a Graphite Electrodes, and the electrode bottom is apart from the about 0.8cm of bottom of electrolytic tank.Constant current carries out electrolytic reaction, current density 1000A/m at 0.9A
2Tap water circulation cool electrolysis cells, control reaction temperature is at 15-17 ℃.GC follows the tracks of reaction, raw material completely dissolve behind about 12h.The light brown mixture rotary evaporation of gained is removed methyl alcohol, and resistates filters, underpressure distillation, the cut of 95-97 ℃/9000Pa of collection, productive rate about 75%.
Embodiment 5
10g KOAc, 120mL methyl alcohol and 16.4g (0.2mol) 2-methyl furan are added in the electrolyzer that has chuck, are stirred to dissolving fully.Installing electrodes, anode are platinum electrode, and negative electrode is a Graphite Electrodes, and the electrode bottom is apart from the about 0.8cm of bottom of electrolytic tank.Constant current carries out electrolytic reaction, current density 600A/m at 0.5A
2Tap water circulation cool electrolysis cells, control reaction temperature is at 15-17 ℃.GC follows the tracks of reaction, raw material completely dissolve behind about 12h.The light brown mixture rotary evaporation of gained is removed methyl alcohol, and resistates filters, underpressure distillation, the cut of 95-97 ℃/9000Pa of collection, productive rate about 73%.
Embodiment 6
6g KOAc, 120mL methyl alcohol and 16.4g (0.2mol) 2-methyl furan are added in the electrolyzer that has chuck, are stirred to dissolving fully.Installing electrodes, anode are platinum electrode, and negative electrode is a stainless steel electrode, and the electrode bottom is apart from the about 0.8cm of bottom of electrolytic tank.Constant current carries out electrolytic reaction, current density 400A/m at 0.4A
2Tap water circulation cool electrolysis cells, control reaction temperature is at 15-17 ℃.GC follows the tracks of reaction, raw material completely dissolve behind about 10h.The light brown mixture rotary evaporation of gained is removed methyl alcohol, and resistates filters, underpressure distillation, the cut of 95-97 ℃/9000Pa of collection, productive rate about 75%.
Claims (2)
1. an electrolytic oxidation prepares 2-methyl-2,5-dimethoxy-2, and the method for 5-dihydrofuran is characterized in that: 2-methyl furan electrolytic oxidation in methanol solution prepares 2-methyl-2,5-dimethoxy-2,5-dihydrofuran.
2. a kind of electrolytic oxidation according to claim 1 prepares 2-methyl-2,5-dimethoxy-2, and the method for 5-dihydrofuran is characterized in that: do not need to use special electrolyzer, use the electrolyzer of single chamber to get final product.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106381505A (en) * | 2016-08-22 | 2017-02-08 | 滕州市天水生物科技有限公司 | Novel process for producing 2-methyl-3-sulfydryl furan |
| CN106987861A (en) * | 2017-04-12 | 2017-07-28 | 东华大学 | A kind of method that electrolytic catalysis prepares 2,5 dimethoxy dihydrofuran |
| CN107675204A (en) * | 2017-10-09 | 2018-02-09 | 王建玲 | The electrolytic catalysis synthetic method of the dihydrofuran of 2,5 dimethoxy 2,5 |
| CN111029270A (en) * | 2019-12-19 | 2020-04-17 | 西安奕斯伟硅片技术有限公司 | Wafer processing method and apparatus |
| CN113073346A (en) * | 2020-01-06 | 2021-07-06 | 万华化学集团股份有限公司 | Electrochemical method for simultaneously preparing o-diol and pyrrole methoxylation products |
| CN113201760A (en) * | 2021-04-22 | 2021-08-03 | 华东理工大学 | Preparation method of 3, 3-dimethoxy-2-butanol |
-
2009
- 2009-07-13 CN CNA2009101575414A patent/CN101597764A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106381505A (en) * | 2016-08-22 | 2017-02-08 | 滕州市天水生物科技有限公司 | Novel process for producing 2-methyl-3-sulfydryl furan |
| CN106987861A (en) * | 2017-04-12 | 2017-07-28 | 东华大学 | A kind of method that electrolytic catalysis prepares 2,5 dimethoxy dihydrofuran |
| CN106987861B (en) * | 2017-04-12 | 2019-02-01 | 东华大学 | A kind of method of electrolytic catalysis preparation 2,5- dimethoxy dihydrofuran |
| CN107675204A (en) * | 2017-10-09 | 2018-02-09 | 王建玲 | The electrolytic catalysis synthetic method of the dihydrofuran of 2,5 dimethoxy 2,5 |
| CN111029270A (en) * | 2019-12-19 | 2020-04-17 | 西安奕斯伟硅片技术有限公司 | Wafer processing method and apparatus |
| CN113073346A (en) * | 2020-01-06 | 2021-07-06 | 万华化学集团股份有限公司 | Electrochemical method for simultaneously preparing o-diol and pyrrole methoxylation products |
| CN113201760A (en) * | 2021-04-22 | 2021-08-03 | 华东理工大学 | Preparation method of 3, 3-dimethoxy-2-butanol |
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