CN105906499A - Environment-friendly synthesis method for cyclically preparing benzoin - Google Patents
Environment-friendly synthesis method for cyclically preparing benzoin Download PDFInfo
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- CN105906499A CN105906499A CN201610438393.3A CN201610438393A CN105906499A CN 105906499 A CN105906499 A CN 105906499A CN 201610438393 A CN201610438393 A CN 201610438393A CN 105906499 A CN105906499 A CN 105906499A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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Abstract
The invention discloses an environment-friendly synthesis method for cyclically preparing benzoin. The method comprises the steps that polyethylene glycol-400, vitamin B1 and anhydrous potassium carbonate are sequentially added into a reactor; after magnetic stirring is carried out for 5 min at room temperature, benzaldehyde is added; after a thin-layer chromatography monitoring reaction is carried out for 3 h, the colourless solution becomes faint yellow; along with the reaction, white solids in a flask are increased, the reaction is finished after 5 h, the solution stands for 10 min and then is filtered, a filter cake is recrystallized with 95% ethyl alcohol to obtain white powdery solids, and the yield is 93%; the filtrate is added into a reaction bottle, anhydrous potassium carbonate and benzaldehyde are added again, a primary circulation reaction is started, the reaction is finished after 5 h, standing and filtering are carried out, a filter cake is recrystallized with 95% ethyl alcohol to obtain white powdery solids, and the yield is 95%; after the circular reaction is totally carried out 15 times, the reaction yield and reaction time are basically not changed. The synthesis method is simple, the reaction cost is low, the catalytic efficiency is high, the yield is high, and environment friendliness is achieved.
Description
Technical field
The present invention relates to chemical products preparing technical field, be specifically related to a kind of circulation and prepare benzoic green conjunction
One-tenth method.
Background technology
Styrax (hexichol hydroxyl ethyl ketone) is the significantly intermediate synthesizing some important natural products, since 1903
Year, A.J.Lapworth has proposed since benzoic conden-sation reaction mechanism, this reaction be considered as always synthesis a-hydroxy-ketone
One of effective method, but, owing to this reaction used catalyst may often be such that potassium cyanide or the Cymag of severe toxicity, to environment, right
Human body has the biggest harm, and this brings the biggest inconvenience to its extensively application, and based on this, finding and exploring preferably has
The catalyst and other reaction condition that are beneficial to benzoic conden-sation reaction enjoy the concern of organic synthesis worker.
After cyanide is as catalyst, many catalyst, such as Cobastab1, triazolium salt, ionic liquid and some
Adorned thiazole salt is used for this reaction in succession, effectively expands reaction substrate scope, not only aromatic aldehyde even some fat
Fat aldehyde also can be smoothed out benzoic conden-sation reaction.In order to preferably promote that benzoic conden-sation reacts, recently, supercritical CO2, super
Sound wave reacts for such the most in succession, and achieves preferable reaction effect.
Cobastab1Being catalyzed benzoic synthesis to be typically with 95% ethanol as reaction dissolvent, 10%NaOH is reaction alkali,
During adding alkali, temperature to be controlled is between-5 DEG C to-10 DEG C, and in course of reaction, bath temperature to be controlled is 75-80 DEG C, bar
Part is more strict, therefore explores and preferably synthesizes benzoic reaction system and remain a significant job, based on this, if
It is particularly necessary that benzoic green synthesis method is prepared in meter one circulation.
Summary of the invention
For not enough present on prior art, the present invention seeks to be to provide circulation under a kind of room temperature to prepare styrax
Green synthesis method, the method synthesis is simple, reasonable in design, can carry out at ambient temperature, and catalytic efficiency is high, productivity
Height, environmental protection, effectively reduce reaction cost, it is easy to promote the use of.
To achieve these goals, the present invention is to realize by the following technical solutions: styrax is prepared in a kind of circulation
Green synthesis method, the steps include: that (1) is sequentially added into 5mL PEG-4000,1g Cobastab in the reactor1、0.4g
Anhydrous potassium carbonate, under room temperature, magnetic agitation is after 5 minutes, adds 5mL (0.04moL) benzaldehyde, thin-layer chromatography monitoring reaction, reaction
After 3h, colourless solution gradually becomes faint yellow, and along with the carrying out of reaction, in flask, white solid gradually increases, after 5h, and reaction
Terminate, stand reaction 10min, filter, filter cake 10mL 95% ethyl alcohol recrystallization is obtained white powdery solid 3.95g, productivity
93%；
(2) filtrate is added in reaction bulb, add 0.4g Anhydrous potassium carbonate and 5mL benzaldehyde again, start circulation for the first time
Reaction, after 5h, reaction terminates, and stands, filters, and filter cake obtains white powdery solid 3.98g, productivity 94% with 95% ethyl alcohol recrystallization；
(3) filtrate is added in reaction bulb, be sequentially added into 0.4g Anhydrous potassium carbonate and 5mL benzaldehyde, start to circulate again；
(4) circular response is after totally 15 times, and reaction yield and reaction time are the most unchanged.
Beneficial effects of the present invention: (1) Cobastab1Easily open loop loses catalytic action in the basic conditions, but in this reaction
Under the conditions of, Cobastab1Good stability can be kept, react the catalytic effect that can keep excellent for 10 days.
(2) this reaction system recycles 15 times, has no that catalysis activity reduces, greatly reduces reaction cost.
(3) this reaction method is without heating, and initial reaction stage, without cooling, the most just can be carried out, and product is received
Rate is high.
(4) environment is had no side effect by this reaction solvent for use and catalyst, is a green reaction, very environmental protection.
Detailed description of the invention
For the technological means making the present invention realize, creation characteristic, reach purpose and be easy to understand with effect, below in conjunction with
Detailed description of the invention, is expanded on further the present invention.
This detailed description of the invention is by the following technical solutions: benzoic green synthesis method prepare in a kind of circulation, and it walks
Suddenly it is: (1) is sequentially added into 5mL PEG-4000,1g Cobastab in the reactor1, 0.4g Anhydrous potassium carbonate, magnetic under room temperature
After power stirs 5 minutes, adding 5mL (0.04moL) benzaldehyde, thin-layer chromatography monitoring reaction, after reaction 3h, colourless solution gradually becomes
For faint yellow, along with the carrying out of reaction, in flask, white solid gradually increases, and after 5h, reaction terminates, and stands reaction 10min,
Filter, filter cake 10mL 95% ethyl alcohol recrystallization is obtained white powdery solid 3.95g, productivity 93%；
(2) filtrate is added in reaction bulb, add 0.4g Anhydrous potassium carbonate and 5mL benzaldehyde again, start circulation for the first time
Reaction, after 5h, reaction terminates, and stands, filters, and filter cake obtains white powdery solid 3.98g, productivity 94% with 95% ethyl alcohol recrystallization；
(3) filtrate is added in reaction bulb, be sequentially added into 0.4g Anhydrous potassium carbonate and 5mL benzaldehyde, start to circulate again；
(4) circular response is after totally 15 times, and reaction yield and reaction time are the most unchanged.
This detailed description of the invention is mainly found that a kind of green solvent-catalyst system being conducive to styrax synthesis,
This system is by PEG-4000, VB1Form with potassium carbonate, use PEG-4000 as reaction dissolvent, coenzyme Cobastab1
For catalyst, under weak base potassium carbonate effect, obtain target product styrax, very well with excellent productivity and simple post processing
Solve that styrax synthesis exists in current industry catalyst toxicity is big or catalyst toxicity is less but synthesis difficulty, consumption
Greatly, catalytic efficiency is low, production cost is high problem, this system can reuse at normal temperatures, not only environmentally safe, reaction
Productivity is high, good product purity, and significantly reduces synthesis cost, prepares styrax for scale and provides a kind of efficient
Synthetic method, has wide market application foreground.
The general principle of the present invention and principal character and advantages of the present invention have more than been shown and described.The technology of the industry
Personnel, it should be appreciated that the present invention is not restricted to the described embodiments, simply illustrating this described in above-described embodiment and specification
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these become
Change and improvement both falls within scope of the claimed invention.Claimed scope by appending claims and
Equivalent defines.
Claims (1)
1. benzoic green synthesis method is prepared in a circulation, it is characterised in that the steps include: (1) the most successively
Add 5mL PEG-4000,1g Cobastab1, 0.4g Anhydrous potassium carbonate, under room temperature, magnetic agitation is after 5 minutes, add 5mL
(0.04moL) benzaldehyde, thin-layer chromatography monitoring reaction, after reaction 3h, colourless solution gradually becomes faint yellow, along with entering of reaction
OK, in flask, white solid gradually increases, and after 5h, reaction terminates, and stands reaction 10min, filters, by filter cake 10mL 95%
Ethyl alcohol recrystallization obtains white powdery solid 3.95g, productivity 93%；
(2) filtrate is added in reaction bulb, add 0.4g Anhydrous potassium carbonate and 5mL benzaldehyde again, start circulation for the first time
Reaction, after 5h, reaction terminates, and stands, filters, and filter cake obtains white powdery solid 3.98g, productivity 94% with 95% ethyl alcohol recrystallization；
(3) filtrate is added in reaction bulb, be sequentially added into 0.4g Anhydrous potassium carbonate and 5mL benzaldehyde, start to circulate again；
(4) circular response is after totally 15 times, and reaction yield and reaction time are the most unchanged.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610438393.3A CN105906499B (en) | 2016-06-20 | 2016-06-20 | One kind circulation prepares benzoic green synthesis method |
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| CN201610438393.3A CN105906499B (en) | 2016-06-20 | 2016-06-20 | One kind circulation prepares benzoic green synthesis method |
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| CN105906499A true CN105906499A (en) | 2016-08-31 |
| CN105906499B CN105906499B (en) | 2018-03-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558628A (en) * | 2018-04-03 | 2018-09-21 | 宁夏医科大学 | Benzoic preparation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774900A (en) * | 2010-01-27 | 2010-07-14 | 扬州大学 | Method for synthesizing benzoin ketone in water phase |
| CN103288609A (en) * | 2013-06-19 | 2013-09-11 | 常州大学 | Preparation method of benzoin product |
| CN103524319A (en) * | 2013-10-22 | 2014-01-22 | 吉林化工学院 | Synthesis method of benzoin |
| CN103936578A (en) * | 2014-04-01 | 2014-07-23 | 常州大学 | Method for preparing benzoin product in mother liquor recycling manner |
| CN104003863A (en) * | 2014-06-16 | 2014-08-27 | 黄山华惠科技有限公司 | Green synthesis method for benzoin |
| CN104817443A (en) * | 2015-03-04 | 2015-08-05 | 上虞佳英化工有限公司 | Benzoin dimethyl ether synthesis process |
-
2016
- 2016-06-20 CN CN201610438393.3A patent/CN105906499B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774900A (en) * | 2010-01-27 | 2010-07-14 | 扬州大学 | Method for synthesizing benzoin ketone in water phase |
| CN103288609A (en) * | 2013-06-19 | 2013-09-11 | 常州大学 | Preparation method of benzoin product |
| CN103524319A (en) * | 2013-10-22 | 2014-01-22 | 吉林化工学院 | Synthesis method of benzoin |
| CN103936578A (en) * | 2014-04-01 | 2014-07-23 | 常州大学 | Method for preparing benzoin product in mother liquor recycling manner |
| CN104003863A (en) * | 2014-06-16 | 2014-08-27 | 黄山华惠科技有限公司 | Green synthesis method for benzoin |
| CN104817443A (en) * | 2015-03-04 | 2015-08-05 | 上虞佳英化工有限公司 | Benzoin dimethyl ether synthesis process |
Non-Patent Citations (2)
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| 何强芳: "VBl催化糠偶姻缩合的研究", 《化学试剂》 * |
| 曾育才等: "微波加热相转移催化安息香缩合反应", 《嘉应学院学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558628A (en) * | 2018-04-03 | 2018-09-21 | 宁夏医科大学 | Benzoic preparation method |
| CN108558628B (en) * | 2018-04-03 | 2021-06-25 | 宁夏医科大学 | Preparation method of benzoin |
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| CN105906499B (en) | 2018-03-13 |
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