CN1600768A - Method for preparing acetal or ketal - Google Patents
Method for preparing acetal or ketal Download PDFInfo
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- CN1600768A CN1600768A CN 03159657 CN03159657A CN1600768A CN 1600768 A CN1600768 A CN 1600768A CN 03159657 CN03159657 CN 03159657 CN 03159657 A CN03159657 A CN 03159657A CN 1600768 A CN1600768 A CN 1600768A
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- ketal
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- ketones
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Abstract
A method for preparing acetal or ketal by taking reaction aldehyde or ketone with alcohol by acid ion liquid as catalyst to prepare acetal or ketal, the ion liquid is used as reaction mediator and catalyst.
Description
Technical field
The present invention relates to a kind of method for preparing acetal or ketal.
Background technology
Ionic liquid at room temperature means in room temperature or is bordering under the room temperature situation molten salt system based on zwitterion, they have Heat stability is good, the liquid temperature wide ranges, steam forces down, can under comparatively high temps, work, multiple organic-inorganic material is all had good dissolving ability, and there are not characteristics such as coordination ability substantially in the ion of composition ionic liquid at room temperature.Ionic liquid at room temperature is as the proton inertia medium, and is not moisture, do not have problems such as aquation, hydrolysis, liberation of hydrogen, avoided the drawback of high-temperature molten salt, also do not resemble inflammable and poorly conductive the organic solvent.The eighties, early stage Britain BP company and French research institutions such as IFP began to explore the possibility of ionic liquid at room temperature as solvent and catalyzer.Simultaneously, because ionic liquid itself has very strong designability, this just makes that we can be according to the different different ionic liquid catalyst system of reaction design.
Alcohol and aldehyde reaction system acetal or ketal are significant process in the organic synthesis, and the method as carbonyl-protection in organic synthesis has purposes widely.Meanwhile, acetal or ketal have caused people's extensive attention as the purposes of reaction intermediate at aspects such as the pure medicine of synthesizing optical, agricultural chemicals, spices.In research in the past, various protonic acids, Lewis acid are used as the catalyzer of acetal or ketal reaction widely.Because this class catalyzer exists equipment corrosion, environmental pollution is serious and Separation and Recovery, reuse problem such as difficulty, research environment close friend how, can reusable acetal or the ketal catalyzer just become the emphasis of people's research.Recently, the title complex of various transition metal and precious metal begins to be used as the catalyzer of acetal or ketal reaction and has obtained good result.But the precious metals complex catalyst system is relatively expensive and decompose easily, and its repeated use is very difficult.From existing bibliographical information, acetal or ketal reaction require catalyzer to have suitable soda acid position and structure, this just make we can according to the requirement of acetal or ketal reaction synthetic new, efficiently, eco-friendly acetal or ketal catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing acetal or ketal.
A kind of method for preparing acetal or ketal, this method use the ionic liquid of acid function to be catalyst aldehydes or ketones and corresponding acetal of pure prepared in reaction or ketal.
The used acid function ionic liquid of the present invention is imidazole salts or pyridinium salt, and wherein imidazole salts cationic structural formula is
The structural formula of the used aldehydes or ketones of the present invention is
The structural formula of the used alcohol of the present invention is
The used aldehydes or ketones of the present invention is 1 with the mol ratio of alcohol: 2-1: 10.
The method of the invention is characterized in that aldehydes or ketones and ion liquid volume ratio are 100: 1-1: 1.
The method of the invention, the temperature of reaction that it is characterized in that this reaction are 0 ℃-50 ℃.
The method of the invention, the reaction times that it is characterized in that this reaction is 0.2-3 hour.
The preparation method of ionic liquid that the present invention is used can be referring to document (P.Bonh te, A.P.Dias, N.Papageorgiou, et al Inorg.Chem.1996,35,1168 and P.A.Z.Suarez, J.E.L.Dulius, S.Einloft, et al Polyhedron 1996,15,1217).
The present invention and traditional catalyst and reaction process relatively have the following advantages:
1. ionic liquid is simultaneously as reaction medium and catalyzer
2. catalyst system is simple, and deionization liquid does not add other solvent and catalyzer outward;
3. operation is simple;
4. separation is simple, purity is high;
5. ionic liquid can recycle.
Embodiment
Embodiment 1-4
2ml butyraldehyde, 5ml primary isoamyl alcohol and 1ml chlorination 1-acetoxyl-3 butyl-imidazole ion liquid are joined in the round-bottomed flask of 25ml.Stirred 1.5 hours in 15 ℃.Analyze its transformation efficiency, selectivity and yield (embodiment 13) then.Ionic liquid is reused 3 times (embodiment 14-16).
The ionic liquid-catalyzed butyraldehyde of table 1 and the primary isoamyl alcohol reaction producing butyladehyde 2-primary isoamyl alcohol that contracts
| Access times | Transformation efficiency | Selectivity | Yield |
| ????1 | ????91 | ????97 | ????89 |
| ????2 | ????92 | ????98 | ????90 |
| ????3 | ????92 | ????97 | ????88 |
| ????4 | ????92 | ????97 | ????89 |
Embodiment 5
2ml butyraldehyde, 5ml primary isoamyl alcohol and 1ml chlorination 1-acetoxyl-3-decyl-imidazole ion liquid are joined in the round-bottomed flask of 25ml.Stirred 2 hours in 15 ℃.Analyze transformation efficiency 83%, selectivity 98%, yield 77%.
Embodiment 6
2ml butyraldehyde, 8ml primary isoamyl alcohol and 1ml trifluoracetic acid-1-acetoxyl-3-butyl imidazole ionic liquid is joined in the round-bottomed flask of 25ml.Stirred 2 hours in 25 ℃.Analyze transformation efficiency 95%, selectivity 98%, yield 93%.
Embodiment 7
1ml octanal, 5ml methyl alcohol and 1ml trifluoracetic acid-1-acetoxyl-3-butyl imidazole ionic liquid is joined in the round-bottomed flask of 25ml.Stirred 2 hours in 25 ℃.Analyze transformation efficiency 73%, selectivity 98%, yield 68%.
Embodiment 8
2ml propionic aldehyde, 5ml n-dodecanol and 2ml fluoroboric acid 1-acetoxyl-3-butyl-imidazole ion liquid are joined in the round-bottomed flask of 25ml.Stirred 3 hours in 20 ℃.Analyze transformation efficiency 63%, selectivity 89%, yield 65%.
Embodiment 9
With 1ml pimelinketone, 5ml hexanol and 1ml fluoroboric acid-1,3-diacetoxyl imidazole ion liquid joins in the round-bottomed flask of 25ml.Stirred 2 hours in 25 ℃.Analyze transformation efficiency 73%, selectivity 98%, yield 68%.
Embodiment 10
2ml phenyl aldehyde, 6ml primary isoamyl alcohol and 2ml trifluoromethanesulfonic acid 1-acetoxyl-3-butyl-imidazole ion liquid are joined in the round-bottomed flask of 25ml.Stirred 3 hours in 30 ℃.Analyze transformation efficiency 46%, selectivity 97%, yield 49%.
Embodiment 11
2ml diphenylketone, 6ml ethanol and 2ml trifluoromethanesulfonic acid 1-acetoxyl-3-butyl-imidazole ion liquid are joined in the round-bottomed flask of 25ml.Stirred 3 hours in 30 ℃.Analyze transformation efficiency 89%, selectivity 97%, yield 87%.
Embodiment 12
2ml methyl phenyl ketone, 6ml phenylcarbinol and 1ml trifluoromethanesulfonic acid 1-sulfonic group-3-butyl-imidazole ion liquid are joined in the round-bottomed flask of 25ml.Stirred 2 hours in 40 ℃.Analyze transformation efficiency 91%, selectivity 99%, yield 86%.
Embodiment 13
2ml phenyl aldehyde, the 8ml trimethyl carbinol and 1ml trifluoromethanesulfonic acid 1-sulfonic group-3-butyl-imidazole ion liquid are joined in the round-bottomed flask of 25ml.Stirred 1 hour in 15 ℃.Analyze transformation efficiency 79%, selectivity 99%, yield 71%.
Claims (7)
1, a kind of method for preparing acetal and ketal is characterized in that using the ionic liquid of acid function to be catalyst aldehydes or ketones and corresponding acetal of pure prepared in reaction or ketal; Wherein the acid function ionic liquid is imidazole salts and pyridinium salt, and the cationic structural formula of imidazole salts is
The cationic structural formula of pyridinium salt is
Wherein a is the integer between the 0-15, and b is the integer between the 0-15; The negatively charged ion of imidazole salts and pyridinium salt is a kind of in chlorine, bromine, iodine, fluoroboric acid root, hexafluorophosphoric acid root, trifluoracetic acid root, acetate and the trifluoromethanesulfonic acid root.
2, method according to claim 1 is characterized in that the structural formula of used aldehydes or ketones is
3, method according to claim 1 is characterized in that the structural formula of used alcohol is
Wherein c is the integer between the 0-14, and d is the integer between 0 to 14.
4, method according to claim 1 is characterized in that the used aldehydes or ketones and the mol ratio of alcohol are 1: 2-1: 10.
5, method according to claim 1 is characterized in that aldehydes or ketones and ion liquid volume ratio are 100: 1-1: 1.
6, method according to claim 1 is characterized in that temperature of reaction is 0 ℃-50 ℃.
7, method according to claim 1 is characterized in that the reaction times is 0.2-3 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03159657 CN1600768A (en) | 2003-09-25 | 2003-09-25 | Method for preparing acetal or ketal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03159657 CN1600768A (en) | 2003-09-25 | 2003-09-25 | Method for preparing acetal or ketal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1600768A true CN1600768A (en) | 2005-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 03159657 Pending CN1600768A (en) | 2003-09-25 | 2003-09-25 | Method for preparing acetal or ketal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011518177A (en) * | 2008-04-18 | 2011-06-23 | ダウ グローバル テクノロジーズ リミティド ライアビリティ カンパニー | Silylimidazolium salt complex |
| CN102249868A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for preparing polymethoxy dimethyl ether by subjecting formaldehyde and methanol to acetalation reaction |
| CN106076409A (en) * | 2016-06-13 | 2016-11-09 | 王金明 | A kind of ionic liquid catalyst of ammoxidation and preparation method thereof |
| CN106866388A (en) * | 2017-01-12 | 2017-06-20 | 中国科学院兰州化学物理研究所 | A kind of method of ionic liquid-catalyzed synthesis diethoxymethane |
| CN107108486A (en) * | 2015-01-09 | 2017-08-29 | 帝斯曼知识产权资产管理有限公司 | The method for producing specific acetal and ketal |
| CN109485809A (en) * | 2018-11-14 | 2019-03-19 | 中国工程物理研究院化工材料研究所 | Ionic liquid-catalyzed solidification pentaerythrite acrolein resin of one kind and preparation method thereof |
-
2003
- 2003-09-25 CN CN 03159657 patent/CN1600768A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011518177A (en) * | 2008-04-18 | 2011-06-23 | ダウ グローバル テクノロジーズ リミティド ライアビリティ カンパニー | Silylimidazolium salt complex |
| CN102249868A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for preparing polymethoxy dimethyl ether by subjecting formaldehyde and methanol to acetalation reaction |
| CN107108486A (en) * | 2015-01-09 | 2017-08-29 | 帝斯曼知识产权资产管理有限公司 | The method for producing specific acetal and ketal |
| CN107108486B (en) * | 2015-01-09 | 2023-06-02 | 帝斯曼知识产权资产管理有限公司 | Process for producing specific acetals and ketals |
| CN106076409A (en) * | 2016-06-13 | 2016-11-09 | 王金明 | A kind of ionic liquid catalyst of ammoxidation and preparation method thereof |
| CN106866388A (en) * | 2017-01-12 | 2017-06-20 | 中国科学院兰州化学物理研究所 | A kind of method of ionic liquid-catalyzed synthesis diethoxymethane |
| CN109485809A (en) * | 2018-11-14 | 2019-03-19 | 中国工程物理研究院化工材料研究所 | Ionic liquid-catalyzed solidification pentaerythrite acrolein resin of one kind and preparation method thereof |
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