CN101148400A - Method for preparing aldehydes and ketones by using oxygen gas to oxidize alcohols - Google Patents
Method for preparing aldehydes and ketones by using oxygen gas to oxidize alcohols Download PDFInfo
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- CN101148400A CN101148400A CNA2006100478451A CN200610047845A CN101148400A CN 101148400 A CN101148400 A CN 101148400A CN A2006100478451 A CNA2006100478451 A CN A2006100478451A CN 200610047845 A CN200610047845 A CN 200610047845A CN 101148400 A CN101148400 A CN 101148400A
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Abstract
The present invention relates to chemical reaction process of oxidizing alcohol with oxygen to prepare aldehyde or ketone, and is especially an alcohol oxidizing process with 2, 2, 6, 6-tetramethyl piperidine nitroxide free radical as catalyst. In organic solvent, and in the presence of catalyst comprising TEMPO, sodium nitrite and transition metal salt, alcohol is oxidized to produce aldehyde or ketone. The process has the alcohol, TEMPO, sodium nitrite and transition metal salt in the weight ratio of 100 to 1-5 to 1-10 to 1-10, oxygen pressure of 0.1-0.8 MPa, reaction temperature of 0-80 deg.c and reaction time of 1-24 hr. The present invention has the advantages of mild reaction condition, easy control, low cost, high safety and environment friendship.
Description
Technical field
The present invention relates to the chemical reaction process by oxygen catalytic oxidation alcohol preparation aldehydes or ketones, specifically a kind ofly utilize 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TEMPO) is as the novel method of the dioxygen oxidation alcohol of catalyzer.
Background technology
It is to be an important unit process in the organic synthesis that alcohol is oxidized to carbonyl compound, and this reaction is widely used in [document 1:Hudlicky, M. in synthesizing of fine chemicals and organic intermediate; Oxidations in Organic Chemistry.Washington, DC:ACS, 1990].Stoichiometric oxygenant, for example chromic oxide [document 2:Muzart, J.Chem.Rev., 1992,92,113-140.], manganese oxide [document 3:Regen, S.L. are adopted in this class reaction traditionally; Koteel, C.J.Am.Chem.Soc., 1977,99,3837-3838.], ruthenium oxide [document 4:Griffith, W.P.Chem.Soc.Rev., 1992,21,179-185], Dess-Martin reagent [document 5:Dess, D.B.; Martin, J.C.J.Org.Chem., 1983,48,4155-4156] etc. oxygenant.Traditional method need be used plurality of heavy metal reagent on the one hand, has increased raw materials cost, on the other hand, a large amount of waste severe contaminations that reaction process produces environment.The environmental pollution that becomes increasingly conspicuous now also is one makes us stubborn problem, so how to address these problems more and more is subject to people's attention.Therefore no matter from the angle of economy, still from the viewpoint of protection environment and Sustainable development, the dioxygen oxidation method that presses for the new green of development substitutes traditional stoichiometry oxidation.
Summary of the invention
In order to overcome the subject matter that above-mentioned brominated systems exists, the purpose of this invention is to provide a kind of reaction conditions gentleness, efficient height, the pure method for preparing aldehydes or ketones of cost oxygen catalytic oxidation low, environmentally safe.
For achieving the above object, the technical solution used in the present invention is:
Under the organic solvent condition, make oxygenant with oxygen, as catalyzer, oxidation alcohol generates aldehydes or ketones with TEMPO, Sodium Nitrite, transition metal salt.
Be specially: in organic solvent, with oxygen or air oxidant, with 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TEMPO), Sodium Nitrite, transition metal salt are as catalyzer, oxidation alcohol generates aldehydes or ketones, alcohol, 2,2,6, the ratio of the amount of substance of 6-tetramethyl piperidine nitrogen oxygen free radical (TEMPO), Sodium Nitrite, transition metal salt is 100: 1-5: 1-10: 1-10, oxygen partial pressure is 0.1-0.8MPa, and temperature of reaction is 0～80 ℃, and the reaction times is 1-24h.
Described solvent is benzene, toluene, methylene dichloride, ethylene dichloride, chloroform, acetonitrile, methyl alcohol, ethanol, acetate, N, one or more mixing in dinethylformamide, the methyl-sulphoxide.
Described catalyzer contains transition metal salt, and transition metal can be one or more in iron, copper, chromium, manganese, the cobalt.
Described alcohol, 2,2,6, the ratio of the amount of the preferred material of 6-tetramethyl piperidine nitrogen oxygen free radical, Sodium Nitrite, transition metal salt is 100: 1-2: 5-8: 5-8.
Described alcohol is fragrant benzylalcohol, contain the heteroatomic fragrant benzylalcohol of N, S, fatty secondary alcohol, alicyclic ring secondary alcohol.
The invention has the beneficial effects as follows:
1. adopt cheap, abundant oxygen instead of chemical oxygenant, reduce raw materials cost effectively.
2. the reaction conditions gentleness operates being easy to control.The present invention is reflected at organic solvent and carries out, and temperature of reaction is controlled at 0～80 ℃, and at room temperature, reaction just can be carried out smoothly.Oxygen pressure is low, and under the 0.1MPa oxygen pressure, reaction just can be advanced smoothly.
3. aftertreatment is simple, the product yield height.
4. whole process is environmentally friendly, does not have pollution.Because used oxygenant is an oxygen in the reaction process, by product is a water, so whole process almost can not cause any pollution to environment, is a kind of green chemical synthesis method.
Embodiment
Give further instruction below by example to the present invention, certainly, the present invention is not limited only to following embodiment.
Embodiment 1
Be reflected in the 316L stainless steel still (300mL) that magneton is housed and carry out with Teflon lining, the air in the still before reaction without replacement of oxygen.Earlier the 10mL methylene dichloride is joined in the autoclave, again 10.0mmol phenylcarbinol and 0.1mmolTEMPO are joined in the 10mL solvent, and then add 0.5mmol FeCl
3, add 0.5mmolNaNO at last
2, sealing.Still is pressurized to 0.1MPa, transfers in the oil bath that rises to 80 ℃ in advance, be reacted to and stop after certain corresponding time to stir, cooling, the careful pressure of putting.After gas chromatographic analysis is carried out in sampling, the liquid in the still is transferred in the separating funnel, carefully washed still then, merge organic solution with methylene dichloride.With saturated Na
2S
2O
3The solution washing organic phase, remove TEMPO and inorganic salt, the organic layer anhydrous sodium sulfate drying, rotary evaporation is removed organic solvent and can be obtained pure phenyl aldehyde, yield 95% then.The GC purity assay is more than 99%.Assay adopts the HP-5890 gas chromatography system, the OV-1701 post (30mm * 0.25mm), hydrogen flame detector, the temperature of monitor is 260 ℃, the temperature of sampler is 260 ℃, furnace temperature adopts temperature programming: earlier at 50 ℃ of constant temperature 5min, be warming up to 250 ℃ with 10 ℃/min then, then at 250 ℃ of constant temperature 10min.The contrast and the gas chromatography retention time of n-compound, GC-MS and
1H-NMR proves conclusively product.
Embodiment 2
Temperature of reaction is a room temperature, and test methods and procedures is with embodiment 1, and the reaction times is 6h, yield 95%.
Embodiment 3
Used transition metal ion is Cu (NO
3)
2, test methods and procedures is with embodiment 1, and temperature of reaction is 80 ℃, and the reaction times is 1h, yield 94%.
Embodiment 4
Used transition metal ion is Cr (NO
3)
3, test methods and procedures is with embodiment 1, and temperature of reaction is 80 ℃, and the reaction times is 1h, yield 92%.
Embodiment 5
Used reactant is to chlorobenzene methanol, and test methods and procedures is with embodiment 1, and temperature of reaction is 80 ℃, and the reaction times is 1h, yield 96%.
Embodiment 6
Used reactant is the 2-hydroxymethyl thiophene, and test methods and procedures is with embodiment 1, and temperature of reaction is a room temperature, and TEMPO is 2mol%, and the reaction times is 6h, yield 92%.
Embodiment 7
Used reactant is the 2-4-hydroxymethylpiperidine, needs in the reaction solution to add 1 milliliter of acetic acid, and test methods and procedures is with embodiment 1, and temperature of reaction is a room temperature, and TEMPO is 2mol%, and the reaction times is 6h, yield 89%.
Embodiment 8
Used reactant is a prenol, and test methods and procedures is with embodiment 1, and temperature of reaction is a room temperature, and TEMPO is 2mol%, and the reaction times is 6h, yield 83%.
Embodiment 9
Used reactant is a sec-n-octyl alcohol, and test methods and procedures is with embodiment 1, and temperature of reaction is a room temperature, and TEMPO is 2mol%, and the reaction times is 6h, yield 89%.
Embodiment 10
Used reactant is the 1-phenylethyl alcohol, and test methods and procedures is with embodiment 1, and temperature of reaction is 80 ℃,, TEMPO is 1mol%, the reaction times is 1h, yield 96%.
Embodiment 11
Used reactant is a styryl carbinol, and test methods and procedures is with embodiment 1, and temperature of reaction is a room temperature, and TEMPO is 2mol%, and the reaction times is 6h, yield 97%.
Embodiment 12
Used reactant is a hexalin, and test methods and procedures is with embodiment 1, and temperature of reaction is a room temperature, and TEMPO is 2mol%, and the reaction times is 6h, yield 91%.
Show by above-mentioned example, adopt oxygen catalytic oxidation alcohol provided by the present invention to prepare the method for aldehydes or ketones, can be widely with the alcohol that contains functional groups such as the two keys of C=C, N, S heteroatoms quantitatively, highly selective is oxidized to corresponding aldehydes or ketones, and can obtains product by high yield.This method has productive rate height, reaction conditions gentleness, and operation is easy to control, cost is low, safe, whole process is environmentally friendly, does not have characteristics such as pollution.
Claims (5)
1. dioxygen oxidation alcohol prepares the method for aldehydes or ketones, it is characterized in that: in organic solvent, with oxygen or air oxidant, with 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, Sodium Nitrite, transition metal salt are as catalyzer, and oxidation alcohol generates aldehydes or ketones, alcohol, 2,2,6, the ratio of the amount of substance of 6-tetramethyl piperidine nitrogen oxygen free radical, Sodium Nitrite, transition metal salt is 100: 1-5: 1-10: 1-10, oxygen partial pressure are 0.1-0.8 MPa, temperature of reaction is 0～80 ℃, and the reaction times is 1-24 h.
2. the method for preparing aldehydes or ketones according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described solvent is benzene, toluene, methylene dichloride, ethylene dichloride, chloroform, acetonitrile, methyl alcohol, ethanol, acetate, N, one or more mixing in dinethylformamide, the methyl-sulphoxide.
3. prepare the method for aldehydes or ketones according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described transition metal can be one or more in iron, copper, chromium, manganese, the cobalt.
4. prepare the method for aldehydes or ketones according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described alcohol, 2,2,6, the ratio of the amount of substance of 6-tetramethyl piperidine nitrogen oxygen free radical, Sodium Nitrite, transition metal salt is 100: 1-2: 5-8: 5-8.
5. prepare the method for aldehydes or ketones according to the described dioxygen oxidation of claim 1 alcohol, it is characterized in that: described alcohol is fragrant benzylalcohol, contain the heteroatomic fragrant benzylalcohol of N, S, fatty secondary alcohol or alicyclic ring secondary alcohol.
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| CN102101826A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or ketone by oxidizing alcohol |
| CN101632941B (en) * | 2008-07-22 | 2011-08-24 | 郑州大学 | Catalyst for preparing aldehydes or ketones by selective oxidation of alcohols with molecular oxygen and application thereof |
| CN102964192A (en) * | 2011-09-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or ketone by alcohol oxidation |
| CN102964191A (en) * | 2011-08-31 | 2013-03-13 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde and ketone by alcohol oxidation |
| CN103191769A (en) * | 2013-04-15 | 2013-07-10 | 陕西煤业化工技术开发中心有限责任公司 | Catalyst for producing benzaldehyde through catalytic oxidation of benzyl alcohol and preparation method thereof |
| CN104119212A (en) * | 2013-04-27 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for catalytically oxidizing 3,3-dimethyl-1-butanol to prepare 3,3-dimethyl-1-butyraldehyde |
| CN104130112A (en) * | 2014-08-05 | 2014-11-05 | 楚澜科技武汉有限公司 | Method and equipment for preparing aldehyde or ketone through continuous oxidization by oxygen |
| JP2015502972A (en) * | 2011-12-22 | 2015-01-29 | ロケット・フルーレ | Improved method for selectively oxidizing 5-hydroxymethylfuraldehyde |
| CN105601559A (en) * | 2014-12-02 | 2016-05-25 | 安徽星宇化工有限公司 | Synthetic method for 2-pyridylaldehyde |
| CN106800492A (en) * | 2015-11-26 | 2017-06-06 | 中国科学院大连化学物理研究所 | A kind of iron catalytic alcohol oxidation prepares the green method of aldehyde or copper |
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| CN101632941B (en) * | 2008-07-22 | 2011-08-24 | 郑州大学 | Catalyst for preparing aldehydes or ketones by selective oxidation of alcohols with molecular oxygen and application thereof |
| CN102101826B (en) * | 2009-12-16 | 2013-07-24 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or ketone by oxidizing alcohol |
| CN102101826A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or ketone by oxidizing alcohol |
| CN102964191A (en) * | 2011-08-31 | 2013-03-13 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde and ketone by alcohol oxidation |
| CN102964191B (en) * | 2011-08-31 | 2014-06-04 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde and ketone by alcohol oxidation |
| CN102964192A (en) * | 2011-09-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or ketone by alcohol oxidation |
| CN102964192B (en) * | 2011-09-01 | 2014-06-04 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or ketone by alcohol oxidation |
| JP2015502972A (en) * | 2011-12-22 | 2015-01-29 | ロケット・フルーレ | Improved method for selectively oxidizing 5-hydroxymethylfuraldehyde |
| CN103191769A (en) * | 2013-04-15 | 2013-07-10 | 陕西煤业化工技术开发中心有限责任公司 | Catalyst for producing benzaldehyde through catalytic oxidation of benzyl alcohol and preparation method thereof |
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