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Method for preparing carboxylic ester by alcohol direct oxidation esterification method

A technology of oxidative esterification and carboxylate, which is applied in the formation/introduction of carboxylate groups, the preparation of carboxylate, chemical instruments and methods, etc. Low activity, cumbersome reaction conditions, etc., to achieve the effect of simple recovery, shortened process steps, and environmental friendliness

Active Publication Date: 2019-05-31
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] Although the catalytic system composed of supported palladium nanometers can realize the oxidative esterification of alcohols, there are still many shortcomings: the reaction needs to add complex ligands and a large number of additives, the reaction conditions are cumbersome, and the yield of the product is low
Although the catalytic system composed of supported gold nanoparticles can realize the oxidative esterification of alcohols, there are still many shortcomings: complex material preparation process, cumbersome nano-gold loading process, and nano-gold particles are easy to aggregate into large particles with low activity. Multiphase systems cannot be recycled effectively, etc.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0030] Preparation of Au-Co composite particle load carrier:

[0031]Mix 10g of 30% silica sol (pH=4.5), 3.0g of aluminum nitrate, 1.2g of magnesium hydroxide, 2.0g of zirconium nitrate, 3g of concentrated nitric acid with a mass concentration of 65%, and 100mL of deionized water, and then stir and mature at 50°C After 24 hours, a solid solution suspension was obtained, and the water was removed by rotary evaporation, and dried under vacuum at 80° C. to obtain a solid. The solid is placed in a tube furnace, and the temperature is programmed to be roasted under air, the temperature is raised at a constant rate of 30-300°C for 3 hours, kept at 300°C for 4 hours, heated at a constant rate of 300-600°C for 3 hours, and kept at 600°C for 4 hours. SiO obtained after natural cooling 2 -MgO-Al 2 o 3 -ZrO 2 Metal composite oxide support.

[0032] Preparation of Au-Co composite particle loads:

[0033] Add 1 g of SiO to the reactor sequentially 2 -MgO-Al 2 o 3 -ZrO 2 The carri...

Embodiment 1

[0034] Embodiment 1: the synthesis of methyl benzoate

[0035] 20mg Au-Co composite particle load (0.1mol%), 13.8mg K 2 CO 3 (10mol%), 108mg benzyl alcohol (1mmol), and 4mL methanol were sequentially added to a 25mL glass-lined autoclave, replaced by oxygen three times, and charged to 0.1MPa, reacted at 80°C for 5h, cooled to room temperature, and slowly released The gas was decompressed, the catalyst was filtered, the filtrate was concentrated by rotary evaporation, and the product methyl benzoate was 123.7 mg after column chromatography of the residue, which was a colorless liquid with a yield of 91%. 1 H NMR (400M, CDCl 3 )δppm: 3.91(s, 3H), 7.43(t, J=7.6Hz, 2H), 7.55(t, J=8.0Hz, 1H), 8.04(d, J=7.6Hz, 2H); 13 C NMR (100M, CDC1 3 ) δppm: 167.1, 132.9, 130.2, 129.6, 128.3, 52.0.

Embodiment 2

[0036] Embodiment 2: the synthesis of methyl p-toluate

[0037] 20mg Au-Co composite particle load (0.1mol%), 13.8mg K 2 CO 3 (10mol%), 122mg p-methylbenzyl alcohol (1mmol), and 4mL methanol were sequentially added to a 25mL glass-lined autoclave, replaced with oxygen three times, and charged to 0.1MPa, reacted at 80°C for 7h, and cooled to room temperature , degassing and depressurization slowly, filter the catalyst, concentrate the filtrate by rotary evaporation, and obtain 135.9 mg of the product methyl p-toluate after column chromatography of the residue, a slightly yellow liquid, and the yield is 91%. 1 H NMR (400M, CDCl 3 )δppm: 2.38(s,3H), 3.89(s,3H), 7.28-7.35(m,2H), 7.82-7.85(m,2H); 13 C NMR (100M, CDCl 3 ) δppm: 167.1, 143.5, 129.6, 129.0, 127.4, 51.8, 21.6.

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PUM

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Abstract

The invention discloses a method for preparing a carboxylic ester by an alcohol direct oxidation esterification method. The method comprises the following steps: taking an aromatic alcohol compound ora saturated linear aliphatic alcohol as a reaction substrate, taking an Au-Co composite particle carrier as a catalyst, adding a low catalytic amount of alkali, reacting for 0.5-15 h in a methanol solvent at the temperature of 25-150 DEG C in air or oxygen or a mixed atmosphere of the air or the oxygen, and performing aftertreatment to obtain a target product carboxylic ester. According to the preparation method disclosed by the invention, the process steps are reduced, conditions are mild, catalyst consumption is less, atom economy is high, the method is simple to operate, the application range of the substrate is wide, and industrial practicability is achieved.

Description

technical field [0001] The invention relates to a method for preparing carboxylate by direct oxidative esterification of alcohol, in particular to a method for preparing carboxylate from alcohol with Au-Co composite particle load as a catalyst. Background technique [0002] Organic methyl carboxylate is a very important class of chemical products and organic synthesis intermediates, widely used in food, organic synthesis, coatings, spices, cosmetics, medicine and polymer materials and other fields. The industrial synthesis method of organic methyl carboxylate mainly contains five classes: 1), the reaction of alcohol phenol and various acylating agents makes ester; 2), carboxylic acid and alcohol, acid, transesterification method of ester; 3) , Halogenated hydrocarbons and CO and alcohol cross-coupling to generate esters; 4), one-step oxidation of aldehydes to generate esters; 5), one-step oxidation of alcohols to generate esters. [0003] Whether it is transesterification o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/40C07C69/78C07C69/76C07C69/618C07C69/24C07D307/68C07B41/12B01J23/89
Inventor 高爽李国松吕迎
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI