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Synthetic method of glyoxylic ester

A synthesis method and glyoxylate technology, applied in the chemical industry, can solve the problems of serious environmental pollution, low content and low product content, and achieve the effects of simple reaction raw materials, avoiding environmental pollution and safe reaction process

Inactive Publication Date: 2016-01-27
HENAN NEWLAND PHARMA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Such a yield is far from meeting the needs of its industrialization, and the reaction process needs to use a strong oxidant, with many side reactions and low purity of the obtained product
[0013] Based on the above routes, the reported schemes all have the disadvantages of expensive raw materials, expensive catalysts and low synthesis yields, resulting in high synthesis costs and difficulty in industrialization.
Inorganic oxidants such as lead acetate and potassium permanganate are used, which are expensive and cause serious environmental pollution, which is not conducive to clean production
The process of deethylating raw materials is difficult to complete, and there are hydrolyzed products of esters, so it is difficult to increase the product content
The oxidation method itself is prone to side reactions and impurities, and the separation of the reaction solvent and glyoxylate is designed, resulting in low product content. Currently, the gas phase content of commercially available ethyl glyoxylate (deducting the toluene peak) is mostly 92%. Up and down, low content

Method used

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  • Synthetic method of glyoxylic ester
  • Synthetic method of glyoxylic ester
  • Synthetic method of glyoxylic ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] The synthesis of embodiment 1 ethyl glyoxylate

[0041] Add 740g (2mol) of 20% glyoxylic acid aqueous solution into the 1L reaction bottle, distill water under reduced pressure until no water is evaporated, and the glyoxylic acid dehydration is completed. After the concentrated glyoxylic acid in the reaction bottle is cooled, add ethanol 92g (2mol), 1.48g of p-toluenesulfonic acid (1% of the mass of glyoxylic acid), 74g of toluene (0.5 times of the mass of glyoxylic acid), put into the reaction bottle, open the cold heating mantle, and heat the reaction solution in the bottle to 60°C for reaction. During the reaction, divide water until no water comes out, and continue to distill to recover toluene. After the toluene has been distilled off, the temperature is lowered to below 25°C. Distill the above residual reaction solution under reduced pressure, maintain the vacuum of the system at 13-15mmHg, and receive the fraction at 65-68°C (theoretical value 64-66.5°C) to o...

Embodiment 2

[0042] The synthesis of embodiment 2 ethyl glyoxylate

[0043]Add 1480g (2mol) of 10% glyoxylic acid aqueous solution into the 1L reaction bottle, distill water under reduced pressure until no water is evaporated, and the glyoxylic acid dehydration is completed. After the concentrated glyoxylic acid in the reaction bottle is cooled, add ethanol 110.4g (2.4mol), 2.96g of hydrochloric acid (2% of the mass of glyoxylic acid), 148g of toluene (1 times the mass of glyoxylic acid), put into the reaction bottle, open the cold heating mantle, and heat the reaction solution in the bottle to 65°C, the reaction was carried out. During the reaction, divide water until no water comes out, and continue to distill to recover toluene. After the toluene has been distilled off, the temperature is lowered to below 25°C. Distill the above residual reaction solution under reduced pressure, maintain the vacuum of the system at 15mmHg, and receive the fraction at 65~68°C (theoretical value 64~66...

Embodiment 3

[0044] The synthesis of embodiment 3 ethyl glyoxylate

[0045] Add 184.1g (2.5mol) of solid glyoxylic acid into a 1L reaction flask, then add 128.8g (2.8mol) of ethanol, 5.92g of phosphoric acid (3% of the mass of glyoxylic acid), 222g of n-hexane (1.2% of the mass of glyoxylic acid) times), put it into the reaction bottle, turn on the cold heating mantle, heat the reaction solution in the bottle to reflux 70°C, and carry out the reaction. During the reaction process, divide water until no water comes out, and continue to distill and recover n-hexane. After the n-hexane has been distilled off, the temperature is lowered to below 25°C. Distill the above residual reaction solution under reduced pressure, maintain the vacuum of the system at 15mmHg, and receive the fraction at 65~68°C (theoretical value 64~66.5°C) to obtain the product. After vacuum distillation, 155.54 g of light yellow viscous liquid was obtained. The theoretical output is 204.18g, the product yield is 76....

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Abstract

The invention relates to the field of chemical engineering, especially to a synthetic method of glyoxylic ester. According to the synthetic method, glyoxalic acid and alcohol undergo an esterification reaction under catalysis of a catalyst in the presence of a water-carrying agent so as to obtain glyoxylic ester. The catalyst is acid, and the water-carrying agent is hydrocarbon. By the synthetic method, yield of a route product is high, content of a gas phase is high, and side reaction is few. There is no need to use heavy metal or other oxidizing agent. The reaction process is safer, and environmental pollution is avoided. Reaction materials are simple and easily available and are common technological raw materials. By the synthetic scheme, synthesis of glyoxylic ester can be industrialized. The synthetic method has cost advantage. Cost of glyoxylic ester is greatly reduced. The synthetic method provides conditions for slathering glyoxylic ester at the industrial level. In addition, quality of the product is better than quality of a commercially available reagent, and gas phase content of the product is far higher than gas phase content 92% of a commercially available reagent.

Description

technical field [0001] The invention relates to the field of chemical industry, in particular to a synthesis method of glyoxylate. Background technique [0002] Ethyl glyoxylate is a common fine chemical, CAS: 924-44-7, its aldehyde group has high chemical activity and is prone to self-polymerization, so the commercially available ethyl glyoxylate is 50% Toluene solution to prevent its polymerization, mainly used in pharmaceutical intermediates, material intermediates. Glyoxylate is a viscous substance with fragrance extracted from plants. Because it has both aldehyde and ester groups, it is an important chemical intermediate in organic synthesis and can carry out a series of chemical reactions , Widely used in the synthesis of medical drugs, varnish dyes, plastic products, flavors and fragrances, and industrial chemical intermediates, such as the preparation of ethyl vanillin, vanillin and allantoin. [0003] There are many synthetic methods of glyoxylic acid esters repor...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/08C07C69/67
Inventor 谢建中刘万军
Owner HENAN NEWLAND PHARMA
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