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Green synthesis process of aryl methyl low-carbonate

A green synthesis technology of methyl carbonate, applied in the formation/introduction of carboxylate groups, preparation of carboxylate esters, preparation of organic compounds, etc., can solve problems such as equipment corrosion and environmental pollution

Active Publication Date: 2015-07-15
惠州市康维健生物科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Regarding the synthesis of aryl methyl subcarbonate, traditional chemical synthesis processes include acid chloride method, concentrated sulfuric acid catalysis method, alkali catalysis method, etc. These several processes all need to wash the product to neutrality with saturated salt water when recovering the product. Therefore, a large amount of high-COD and high-salt wastewater will be produced, which will not only cause corrosion of equipment, but also cause extremely serious pollution to the environment.

Method used

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  • Green synthesis process of aryl methyl low-carbonate
  • Green synthesis process of aryl methyl low-carbonate
  • Green synthesis process of aryl methyl low-carbonate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Embodiment 1, the preparation of ibuprofen methyl ester

[0019]

[0020] Take a 100mL three-neck round bottom flask, add 20.6g (0.1mol) ibuprofen, 0.2g p-toluenesulfonic acid, 40.35mL (1mol) methanol, 20mL (0.274mol) glycerin, stir, and heat the heating mantle to reflux at 70°C for 4hr. After the reaction was finished, unreacted methanol was removed by distillation under normal pressure at 75°C. Put it in a separatory funnel and let it stand for stratification, the upper layer is the methyl ester layer, and the lower layer is the glycerol layer. The glycerol layer was returned to the reaction bottle for recycling in the next round of reaction. The methyl ester layer is separated in a simulated moving bed chromatographic separation system composed of silica gel as an adsorbent and dichloromethane as an eluent to obtain ibuprofen, p-toluenesulfonic acid components and ibuprofen methyl ester components. Dichloromethane was recovered by atmospheric distillation to obt...

Embodiment 2

[0023] Embodiment 2, the preparation of ketoprofen methyl ester

[0024]

[0025] Take a 100mL three-neck round bottom flask, add 25.4g (0.1mol) ketoprofen, 0.5g methanesulfonic acid, 100mL (2.48mol) methanol, 50mL (0.69mol) glycerin, stir, and heat the heating mantle to reflux at 75°C for 6hr. The unreacted methanol was distilled off under reduced pressure at 30°C. Put it in a separatory funnel and let it stand for stratification, the upper layer is the methyl ester layer, and the lower layer is the glycerol layer. The glycerol layer was returned to the reaction bottle for recycling in the next round of reaction. The methyl ester layer is separated in a simulated moving bed chromatographic separation system composed of polyamide as an adsorbent and methyl tert-butyl ether as an eluent to obtain ketoprofen, methanesulfonic acid components and ketoprofen methyl ester group point. Atmospheric pressure distillation reclaimed methyl tert-butyl ether to obtain 26.01 g of keto...

Embodiment 3

[0028] The preparation of embodiment 3,2-methyl phenylpropionate

[0029]

[0030] Take a 100mL three-necked round bottom flask, add 30.40g (0.2mol) 2-phenylpropionic acid, 0.03g Novozym435, 30mL (0.74mol) methanol, 10mL (0.14mol) glycerin, stir, and heat at 55°C for 8hr. The unreacted methanol was distilled off under reduced pressure at 30°C. Filter to remove lipase, place in a separatory funnel to stand for stratification, the upper layer is the methyl ester layer, and the lower layer is the glycerol layer. The glycerol layer was returned to the reaction bottle for recycling in the next round of reaction. The methyl ester layer is separated in a simulated moving bed chromatographic separation system composed of silica gel as an adsorbent and dichloromethane as an eluent to obtain 2-phenylpropionic acid components and 2-phenylpropionic acid methyl ester components. Atmospheric pressure distillation recovered chloroform to obtain 29.90 g of methyl 2-phenylpropionate, and ...

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Abstract

The invention belongs to the field of organic synthesis technique, and particularly relates to a green synthesis process of aryl methyl low-carbonate. The process is suitable for aryl low-carbonate, particularly for the synthesis of methyl esters of various non-steroidal anti-inflammatory drugs such as ibuprofen. The invention provides a universally applicable clean production process of aryl methyl carbonate. Through applying water absorption and polarity of glycerol and combining adoption of separation technique of simulated moving bed chromatography, the process simplifies treatment of reaction mixture, ensures complete separation of reaction product and the rest impurities such as surplus reaction raw materials, solves the problems of recycling of the surplus reaction raw materials, catalyst and water absorbent glycerol, can acquire product with high purity under the premises of water washing-free, no rectification and no three wastes, increases conversion rate of the raw material and yield of the product to be close to 100%, largely reduces production cost, achieves zero release of waste water and waste residue during the product production process, and has a broad application prospect in the fields of medicine, fine chemical industry and the like.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a green synthesis process of aryl methyl subcarbonate. Background technique [0002] Aryl methyl subcarbonate is widely used in fine chemicals and is a very common type of flavor and fragrance. Some of them, such as methyl salicylate, are mainly used as fragrances for medicines; some, such as methyl phenylacetate, cinnamon Acetate methyl ester, etc., are food flavors and daily chemical flavors. [0003] At the same time, methyl aryl subcarbonate is also a class of important pharmaceutical intermediates, some of which, such as methyl salicylate and diclofenac methyl [1], can be used as raw materials by themselves, and some, such as ibuprofen methyl [ 2], which is an important intermediate for chiral resolution. Therefore, it is of great significance to study and improve the synthetic method of methyl aryl ethyl (propionate) to realize the greening and environmental fri...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B41/12C07C69/612C07C67/08C07C69/738C07C69/614C07C69/618C07C69/88C07C69/78C07C69/616C07C69/734C07D209/28C07D491/052C12P7/62C12P17/10C12P17/18
CPCY02P20/54
Inventor 汤鲁宏曹雅晴滕霏赵桧桧
Owner 惠州市康维健生物科技有限公司
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