CN101768064B - Method for preparing aromatic aldehyde employing oxygen to catalyze and oxidize aromatic primary alcohol - Google Patents
Method for preparing aromatic aldehyde employing oxygen to catalyze and oxidize aromatic primary alcohol Download PDFInfo
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- CN101768064B CN101768064B CN 200810230244 CN200810230244A CN101768064B CN 101768064 B CN101768064 B CN 101768064B CN 200810230244 CN200810230244 CN 200810230244 CN 200810230244 A CN200810230244 A CN 200810230244A CN 101768064 B CN101768064 B CN 101768064B
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Abstract
Disclosed is an aromatic aldehyde preparation method employing oxygen to catalyze and oxidize aromatic primary alcohol; the method takes air or oxygen as the oxygen source and adopts the catalyst system composed of vanadium oxides and nitrogen-containing compounds to selectively and highly oxidize the aromatic primary alcohol into corresponding aromatic aldehyde at temperature of 30-120 DEG C. The method has high oxidation efficiency, less side products, mild reaction conditions, has cheap and obtainable catalyst, is easy to separate and purify products, has high practicality and economy.
Description
Technical field
The present invention relates to a kind of catalyze and oxidize aromatic primary alcohol and prepare the method for corresponding aromatic aldehyde.A kind of specifically catalyst system of use two components is an oxygen source with air or oxygen, and high-activity high-selectivity oxidation fragrance primary alconol prepares corresponding aromatic aldehyde under mild conditions.
Background technology
It is one of basic functional group conversion reaction important in the organic chemistry that the aromatic alcohol oxidation prepares aromatic aldehyde, has important application in fine chemistry industry industries such as pharmacy.It is a difficult point as the catalytic oxidation system of the efficient economy of oxygen source that oxygen is used in exploitation always.In the past few decades, scientific worker both domestic and external has successively developed very many catalytic oxidation systems.But wherein most of catalyst system uses precious metal, as palladium, and ruthenium, gold, platinum etc., and this class system usually also needs expensive organic ligand, perhaps needs the extra alkali that adds metering to keep catalyst activity and selectivity of product.So this class catalytic oxidation system cost height, practicality is very limited.Another kind of representational catalytic oxidation system is to use nitroxyl free radical, and representation compound is as 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TEMPO).Report as, triphenyl phosphorus ruthenium chloride/TEMPO, Chinese patent CN1796349A, CN1789225A have reported NaNO respectively
2/ Br
2/ TEMPO, NaNO
2/ HCl/TEMPO, this class system has very high catalytic activity, but halogen corrosive is strong, and easy and alcohol generation halo by product.Nitroxyl free radical as TEMPO, costs an arm and a leg, and is unfavorable for that as organism product separates.Therefore, develop a kind of oxygen or air of using and be oxygen source, do not use precious metal or halogen, low temperature, efficient, cheap catalyze and oxidize aromatic primary alcohol prepare the new technology of aromatic aldehyde simultaneously, have great importance and application background.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing aromatic aldehyde with oxygen to catalyze and oxidize aromatic primary alcohol, use molecular oxygen to be oxygen source, catalytic activity and selectivity of product height, the reaction conditions gentleness, catalyzer is cheap and easy to get, catalyzer separates simply this preparation method's green economy environmental protection with product simultaneously.
For achieving the above object, catalyst system provided by the invention is made up of two kinds of components.
A kind of method of using oxygen to catalyze and oxidize aromatic primary alcohol to prepare aromatic aldehyde is an oxygenant with the air or oxygen, and under katalysis, highly selective is oxidized to corresponding aroma aldehyde with fragrant primary alconol under mild conditions;
Described catalyzer is the two component complex catalyst systems that oxyvanadium compound and nitrogenous compound are formed, first kind of component is oxyvanadium compound: can be vanadylic sulfate, vanadium phosphorus oxide, vanadium oxytrichloride, in the nitric acid vanadyl one or more, the vanadylic sulfate of preferred cheap safety, the consumption of oxyvanadium compound is the 0.5-20.0mol% of fragrant primary alconol; Be preferably 1.0-10.0mol%.
Second kind of component is nitrogenous compound: be meant in Sodium Nitrite, potassium nitrite, lithium nitrite, SODIUMNITRATE, saltpetre, nitric acid, the nitrous ester isopentyl ester one or more, or in reaction process, can form the nitrogenous compound of NO, the nitrogenous compound consumption is the 0.5-20.0mol% of fragrant primary alconol, preferred 1.0-10.0mol%.
The present invention prepares corresponding aromatic aldehyde with above-mentioned catalyst system catalyze and oxidize aromatic primary alcohol, and the key step of its method has:
Catalyst system and fragrant primary alconol are dropped in the reactor, add proper amount of solvent, be warming up to 30-120 ℃, oxygen partial pressure is 0.01-2.0MPa, reaction times 0.5-10.0 hour.
When catalyst levels increased, transformation time shortened fully, but cost up.
Begin to add less water in the forward direction solvent in oxidizing reaction, the volume ratio of water and solvent is 0.05-2.0%, preferred 0.1-1.0%.The solvent of selecting is an acetonitrile, cyanobenzene, succinonitrile, methylene dichloride etc., preferred acetonitrile; Volume is 0.5-100 a times of fragrant primary alconol volume.
The used oxygen source of oxidizing reaction is oxygen or air, wherein oxygen partial pressure 0.01-2.0MPa.
The present invention has following characteristics:
System can highly selective, and the high conversion catalyze and oxidize aromatic primary alcohol prepares aromatic aldehyde, the product yield height.Catalyst levels is few in the reaction system, the reaction conditions gentleness; Oxygen or air are oxygenant, green economy; The oxidising process easy handling, the product catalyst separating is simple.Compare with the great majority report, maximum characteristics of the present invention are: do not use precious metal or halogen, catalyzer is cheap, be simple and easy to, have very high practical value.
Description of drawings
Fig. 1: phenyl aldehyde
1H NMR (DMSO-d
6);
Fig. 2: phenyl aldehyde
13C NMR (DMSO-d
6);
Fig. 3: paranitrobenzaldehyde
1H NMR (DMSO-d
6);
Fig. 4: paranitrobenzaldehyde
13C NMR (DMSO-d
6).
Embodiment
Describe the present invention in detail below by embodiment:
Embodiment 1: with the 5.4g phenylcarbinol, 0.427g vanadylic sulfate, 0.175g Sodium Nitrite join in the 500mL reactor, add the 50mL acetonitrile, add 250 μ L water, close still, charging into oxygen pressure is 0.5MPa, is warming up to 80 ℃ under stirring, and keep 2h, if oxygen partial pressure descends supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and the phenylcarbinol transformation efficiency is greater than 99%, and the phenyl aldehyde selectivity is greater than 98%.Phenyl aldehyde separation yield 93%.Warp
1HNMR,
13CNMR, GC-MS determine it is phenyl aldehyde.
Embodiment 2: with the 5.4g phenylcarbinol, 0.427g vanadylic sulfate, 0.175g Sodium Nitrite join in the 500mL reactor, add the 50mL acetonitrile, close still, charging into oxygen pressure is 0.5MPa, is warming up to 80 ℃ under stirring, and keep 2h, if oxygen partial pressure descends supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, phenylcarbinol transformation efficiency 11.3%, and the phenyl aldehyde selectivity is greater than 98%.
Embodiment 3: with the 5.4g phenylcarbinol, 0.427g vanadylic sulfate, 0.253g potassium nitrite join in the 500mL reactor, add the 50mL acetonitrile, add 500 μ L water, close still, charging into oxygen pressure is 0.5MPa, is warming up to 50 ℃ under stirring, and keep 10h, if oxygen partial pressure descends supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and transformation efficiency is greater than 99%, and selectivity is greater than 98%.
Embodiment 4: with the 5.4g phenylcarbinol, and the 0.213g vanadium phosphorus oxide, the 0.100g SODIUMNITRATE joins in the 500mL reactor, adds the 50mL acetonitrile, add 100 μ L water, close still, charging into oxygen pressure is 0.5MPa, is warming up to 80 ℃ under stirring, and keep 20h, if oxygen partial pressure descends supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and the phenylcarbinol transformation efficiency is greater than 95%, and the phenyl aldehyde selectivity is greater than 98%.
Embodiment 5: with the 5.4g phenylcarbinol, and the 0.427g vanadylic sulfate, 0.286g nitric acid (65%) joins in the 500mL reactor, adds the 50mL acetonitrile, add 250 μ L water, close still, charging into oxygen pressure is 0.5MPa, is warming up to 80 ℃ under stirring, and keep 4h, if oxygen partial pressure descends supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and the phenylcarbinol transformation efficiency is greater than 99%, and the phenyl aldehyde selectivity is greater than 98%.
Embodiment 6: with 6.1g to methylbenzyl alcohol, 0.427g vanadylic sulfate, 0.368g Isopentyl nitrite join in the 500mL reactor, add the 50mL acetonitrile, add 200 μ L water, close still, add 20 μ L water, charging into oxygen pressure is 0.5MPa, be warming up to 80 ℃ under stirring, and keep 2h, if oxygen partial pressure descends supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and near 100%, the p-tolyl aldehyde selectivity is greater than 99% to the methylbenzyl alcohol transformation efficiency.P-tolyl aldehyde separation yield 90%.
Embodiment 7: with 7.6g p-nitrophenyl methyl alcohol, 0.427g vanadylic sulfate, 0.175g Sodium Nitrite joins in the 500mL reactor, adds the 50mL acetonitrile, closes still, add 200 μ L water, charging into oxygen pressure is 0.5MPa, is warming up to 80 ℃ under stirring, and keeps 2h, if oxygen partial pressure descends, supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and the p-nitrophenyl methanol conversion is near 100%, and the paranitrobenzaldehyde selectivity is greater than 99%.Paranitrobenzaldehyde separation yield 94%.Warp
1HNMR,
13CNMR determines it is paranitrobenzaldehyde.
Embodiment 8: with chlorobenzene methanol between 7.1g, 0.427g vanadylic sulfate, 0.175g Sodium Nitrite joins in the 500mL reactor, adds the 50mL succinonitrile, adds 1000 μ L water, close still, charging into oxygen pressure is 0.5MPa, is warming up to 80 ℃ under stirring, and keeps 2h, if oxygen partial pressure descends, supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and a chlorobenzene methanol transformation efficiency is greater than 99%, and the m chlorobenzaldehyde selectivity is greater than 99%.
Example 9: with the adjacent chlorobenzene methanol of 7.1g, 0.427g vanadylic sulfate, 0.175g Sodium Nitrite joins in the 500mL reactor, adds the 50mL cyanobenzene, adds 100 μ L water, close still, charging into oxygen pressure is 0.2MPa, is warming up to 100 ℃ under stirring, and keeps 12h, if oxygen partial pressure descends, supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and adjacent chlorobenzene methanol transformation efficiency is near 100%, and the o-chlorobenzaldehyde selectivity is greater than 99%.
Embodiment 10: with 6.9g meta-methoxy phenylcarbinol, 0.427g vanadylic sulfate, 0.175g Sodium Nitrite joins in the 500mL reactor, adds the 50mL methylene dichloride, adds 200 μ L water, close still, charging into oxygen pressure is 0.5MPa, is warming up to 80 ℃ under stirring, and keeps 2h, if oxygen partial pressure descends, supplemental oxygen.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, meta-methoxy phenylcarbinol transformation efficiency 98%, and the NSC 43794 selectivity is greater than 99%.
Embodiment 11: the abbreviation reaction scale, with 0.76g p-nitrophenyl methyl alcohol, 0.0427g vanadylic sulfate, 0.0175g Sodium Nitrite joins in the 50mL reactor, add the 5mL acetonitrile, close still, add 20 μ L water, charge into air, pressure is 0.6MPa, is warming up to 90 ℃ under stirring, and keeps 1.5h, if if air consumption replenishes air.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and the p-nitrophenyl methanol conversion is near 100%, and the paranitrobenzaldehyde selectivity is greater than 99%.
Embodiment 12: with 1.68g 3, the 4-3,5-dimethoxybenzoic alcohol, 0.0427g vanadylic sulfate, 0.0175g Sodium Nitrite join in the 50mL reactor, add the 5mL acetonitrile, close still, add 25 μ L water, charging into air pressure is 1.0MPa, be warming up to 80 ℃ under stirring, and keep 10h, if air consumption replenishes air.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and 3,4-dimethoxy benzaldehyde transformation efficiency 97%, 3,4-dimethoxy benzaldehyde selectivity is greater than 99%
Embodiment 13: with 1.98g 2,4-dinitrobenzene methyl alcohol, 0.0427g vanadylic sulfate, 0.0175g Sodium Nitrite join in the 50mL reactor, add the 10mL acetonitrile, close still, add 20 μ L water, charging into air pressure is 1.0MPa, be warming up to 90 ℃ under stirring, and keep 5h, if air consumption replenishes air.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, and 2,4-dinitrobenzal-dehyde transformation efficiency 95%, 2,4-dinitrobenzal-dehyde selectivity is greater than 97%.
Embodiment 14: with 2.31g 2-bromo-4-oil of mirbane methyl alcohol, 0.0427g vanadylic sulfate, 0.0175g Sodium Nitrite joins in the 50mL reactor, adds the 20mL acetonitrile, closes still, add 50 μ L water, charging into air pressure is 1.0MPa, is warming up to 90 ℃ under stirring, and keeps 4h, if air consumption replenishes air.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, 2-bromo-4-nitrobenzoyl alcohol conversion 90%, and 2-bromo-4-nitrobenzaldehyde selectivity is greater than 99%.
Embodiment 15: with the 1.54g VANILLYL ALCOHOL MIN 98, and the 0.0427g vanadylic sulfate, the 0.0200g SODIUMNITRATE joins in the 50mL reactor, adds the 10mL acetonitrile, close still, add 50 μ L water, charging into air pressure is 0.5MPa, is warming up to 90 ℃ under stirring, and keep 10h, if air consumption replenishes air.After reaction finishes, cool to room temperature.Gas chromatographic analysis is used in sampling, VANILLYL ALCOHOL MIN 98 transformation efficiency 89%, and the Vanillin selectivity is greater than 99%.
The separated product nucleus magnetic resonance is identified that the result is shown in Fig. 1-4.
Claims (6)
1. a method of using oxygen to catalyze and oxidize aromatic primary alcohol to prepare aromatic aldehyde is characterized in that: be oxygenant with the air or oxygen, under katalysis, under mild conditions fragrant primary alconol be oxidized to corresponding aroma aldehyde;
Described catalyzer is the two component complex catalyst systems that oxyvanadium compound and nitrogenous compound are formed, and the consumption of oxyvanadium compound is the 0.5-20.0mol% of fragrant primary alconol, and the nitrogenous compound consumption is the 0.5-20.0mol% of fragrant primary alconol;
Described oxyvanadium compound is meant one or more in vanadylic sulfate, vanadium phosphorus oxide, vanadium oxytrichloride, the nitric acid vanadyl;
Described nitrogenous compound is meant one or more in Sodium Nitrite, potassium nitrite, lithium nitrite, SODIUMNITRATE, saltpetre, nitric acid, the nitrous ester isopentyl ester, or can form the nitrogenous compound of NO in reaction process.
2. method according to claim 1 is characterized in that: the used oxygen source of oxidizing reaction is air or oxygen, oxygen partial pressure 0.01-2.0MPa wherein, and temperature of reaction is 30-120 ℃, the reaction times is 0.5-10.0 hour.
3. method according to claim 1 is characterized in that: described oxidizing reaction is carried out in organic solvent, and described organic solvent is acetonitrile, cyanobenzene, succinonitrile or dichloromethane solvent; Volume is 0.5-100 a times of fragrant primary alconol volume.
4. according to claim 1 and 3 described methods, it is characterized in that: begin to add less water in the forward direction solvent in oxidizing reaction, the volume ratio of water and solvent is 0.05-2.0%.
5. method according to claim 1 is characterized in that: fragrant primary alconol is the fragrant primary alconol that contains substituted radical on the phenyl ring, described substituted radical specifically can be alkyl ,-Cl ,-Br ,-NO
2, methoxyl group or hydroxyl.
6. method according to claim 5 is characterized in that: substituent position can be one or more in ortho position, a position, the contraposition, and the substituting group kind can be one or several, and the substituting group number can be one or more.
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| CN102060710B (en) * | 2010-12-10 | 2013-11-06 | 合肥工业大学 | High-selectivity synthesis method of O-nitrobenzaldehyde |
| CN104341280A (en) * | 2013-07-25 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde and ketone through alcohol oxidation |
| CN105001065A (en) * | 2015-07-28 | 2015-10-28 | 辽宁石油化工大学 | Method for preparing benzaldehyde through catalyst for benzyl alcohol oxidation |
| CN106008189B (en) * | 2016-05-23 | 2018-10-02 | 昆明理工大学 | A kind of catalyzed conversion veratryl alcohol is the method for veratraldehyde |
| CN108947776B (en) * | 2017-05-18 | 2021-04-30 | 中国科学院大连化学物理研究所 | Method for catalyzing oxidative cracking of lignin model aryl ether |
| CN108503545B (en) * | 2018-04-19 | 2021-05-25 | 大连理工大学 | Method for preparing phenylacetate by catalytic oxidation of mandelate |
| CN118005492B (en) * | 2024-04-08 | 2024-06-11 | 天津农学院 | Method for preparing benzaldehyde by friction catalytic oxidation of benzyl alcohol based on barium strontium titanyl oxalate |
Citations (2)
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| CN1789225A (en) * | 2004-12-16 | 2006-06-21 | 中国科学院大连化学物理研究所 | Method for preparing aromatic aldehyde ketone by utilizing air as oxidant in hydro solvent system |
| CN1796349A (en) * | 2004-12-30 | 2006-07-05 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde and ketone by catalyzing and oxidizing alcohol in air |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789225A (en) * | 2004-12-16 | 2006-06-21 | 中国科学院大连化学物理研究所 | Method for preparing aromatic aldehyde ketone by utilizing air as oxidant in hydro solvent system |
| CN1796349A (en) * | 2004-12-30 | 2006-07-05 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde and ketone by catalyzing and oxidizing alcohol in air |
Non-Patent Citations (2)
| Title |
|---|
| "Selective Aerobic Oxidation of Alcohols with a Combination of a Polyoxometalate and Nitroxyl Radical as Catalysts";Revital Ben-Daniel et al.;《J. Org. Chem.》;20011116;第66卷(第25期);第8650-8653页 * |
| Revital Ben-Daniel et al.."Selective Aerobic Oxidation of Alcohols with a Combination of a Polyoxometalate and Nitroxyl Radical as Catalysts".《J. Org. Chem.》.2001,第66卷(第25期),第8650-8653页. |
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