Greening method for preparing aldehydes and ketones through alcohol oxidation of copper catalyst

A catalytic alcohol, green technology, applied in chemical instruments and methods, preparation of carbon-based compounds, preparation of organic compounds, etc., can solve problems such as high toxicity, limited application potential, and impact on applications

Inactive Publication Date: 2013-12-04
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, many methods still require the use of noble metal catalysts, highly dangerous pure oxygen as the oxidant, and some methods require the use of highly toxic solvents, so the application potential is limited
So far, there are not many catalytic aerobic alco

Method used

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  • Greening method for preparing aldehydes and ketones through alcohol oxidation of copper catalyst
  • Greening method for preparing aldehydes and ketones through alcohol oxidation of copper catalyst
  • Greening method for preparing aldehydes and ketones through alcohol oxidation of copper catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Oxidation of benzyl alcohol to benzaldehyde

[0024]

[0025] Weigh CuI (0.0038g, 1mol%), 2,2'-bipyridine (0.0031g, 1mol%), TEMPO (0.0063g, 2mol%), pyrrolidine (0.0033mL, 2mol%), benzyl alcohol (0.2163g , 2mmol) into an ordinary reactor, add acetonitrile (0.5mL) as a solvent, open the reaction at room temperature (about 25°C), and then track and detect the reaction with GC-MS or TLC. After about 12 hours, the reaction is over, and the mixture is concentrated Afterwards, use petroleum ether and ethyl acetate as developing solvents for flash column chromatography (silica gel as stationary phase) for separation to obtain benzaldehyde with a separation yield of 94%. 1 HNMR (500MHz, CDCl 3 ):δ9.98(s,1H),7.87-7.84(m,2H),7.61-7.57(m,1H),7.50-7.47(t,J=7.5Hz,2H). 13 C NMR (125.4MHz, CDCl 3 ):δ192.5,136.3,134.5,129.7,129.0.MS(EI):m / z(%)107(7),106(100),105(94),78(13),77(87),76( 4),75(3),74(6),52(7),51(28),50(14).

Embodiment 2

[0027] Oxidation of 4-chlorobenzyl alcohol to 4-chlorobenzaldehyde

[0028]

[0029] Sequentially weigh CuI (0.0190g, 5mol%), 2,2'-bipyridine (0.0156g, 5mol%), TEMPO (0.0315g, 10mol%), pyrrolidine (0.0165mL, 10mol%), 4-chlorobenzyl alcohol (0.2852g, 2mmol) into a common reactor, add acetonitrile (0.5mL) as a solvent, open the reaction at room temperature (about 25°C), then track and detect the reaction with GC-MS or TLC, and the reaction is over after about 24 hours , the mixture was concentrated and separated by flash column chromatography using petroleum ether and ethyl acetate as the developing solvent (silica gel as the stationary phase) to obtain 4-chlorobenzaldehyde with a separation yield of 70%. 1 HNMR (500MHz, CDCl 3 ):δ9.99(s,1H),7.84-7.81(dt, 1 J=8.5Hz, 2 J=2.0Hz,2H),7.53-7.50(dt, 1 J=8.5Hz, 2 J=2.0Hz,2H). 13 CNMR (125.4MHz, CDCl 3 ):δ190.8,141.0,134.8,130.9,129.5.MS(EI):m / z(%)142(2),141(24),140(36),139(75),138(100),112( 16), 111(7), 110(49), 84(3), 76(13...

Embodiment 3

[0031] 4-Fluorobenzyl alcohol as 4-fluorobenzaldehyde

[0032]

[0033] Sequentially weigh CuI (0.0038g, 1mol%), 2,2'-bipyridine (0.0031g, 1mol%), TEMPO (0.0063g, 2mol%), pyrrolidine (0.0033mL, 2mol%), 4-fluorobenzyl alcohol (0.2482g, 2mmol) into a common reactor, add acetonitrile (0.5mL) as a solvent, open the reaction at room temperature (about 25°C), then track and detect the reaction with GC-MS or TLC, and the reaction ends after about 12 hours , the mixture was concentrated and separated by flash column chromatography using petroleum ether and ethyl acetate as the developing solvent (silica gel as the stationary phase) to obtain 4-fluorobenzaldehyde with a separation yield of 75%. 1 HNMR (500MHz, CDCl 3 ):δ9.93(s,1H),7.74(d,J=8Hz,2H),7.29(d,J=8Hz,2H),2.40(s,3H). 13 CNMR (125.4MHz, CDCl 3 ):δ191.9,145.5,134.3,129.8,129.7,21.8.MS(EI):m / z(%)125(8),124(94),123(100),96(13),95(83), 94(5),76(3),75(22),74(7),70(6),69(6),68(4),63(2),57(3),51(6), 50(12).

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Abstract

The invention provides a greening method for preparing aldehydes and ketones through the alcohol oxidation of a copper catalyst. The greening method comprises the following steps: taking copper salt as the catalyst, a single-tooth or double-teeth N ligand as the ligand and an organic nitric oxide compound as a co-catalyst, and performing the alcohol aerobic oxidation reaction in water-phase or organic solvent under the existence of alkali and air to prepare an aldehyde and Ketone compound. A copper catalyst system, which is low in cost, easy to obtain, low in toxicity and high in activity, is adopted in the greening method, air is used as an economic, safe and green oxidant, and under the mild condition of the indoor temperature air, the aldehyde and ketone compound is prepared through effective alcohol oxidation. The reaction condition is simple and mild, the operation is easy, the reaction conversion rate is high, the product separation and purification are simple, and the recovery rate is high. The requirement on the reaction condition is relatively low, and the greening method has a good research and industrial application prospect.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a green method for preparing aldehyde or ketone compounds through copper catalysis, air as an oxidant, and aerobic oxidation of alcohol. Background technique [0002] Alcohols are a class of organic compounds with a wide range of sources and low prices. However, due to their stable properties, it is difficult to directly participate in organic reactions. They often need to be converted into more active aldehydes, ketones or halogenated hydrocarbons for synthesis. Therefore, many aldehydes and ketones are prepared by oxidation of alcohols. The traditional method of oxidizing alcohols to synthesize aldehydes and ketones usually uses a large number of oxidants, such as oxidants such as chromium oxide, manganese dioxide, and periodic salts, or uses dangerous hydrogen peroxide, etc., so these methods still have many shortcomings, such as metal Oxides are highly toxic, ge...

Claims

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Application Information

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IPC IPC(8): C07B41/06C07C45/37C07C47/54C07C47/55C07C47/575C07C47/542C07C49/786C07C49/784C07C47/546C07C49/78C07C205/44C07C201/12C07C223/06C07C221/00
Inventor 徐清田海雯尹新林张鹏飞
Owner WENZHOU UNIVERSITY
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