Electrochemical synthesis method of beta-acetamido carbonyl compound

Abstract

The invention discloses an electrochemical synthesis method of a beta-acetamido carbonyl compound, and belongs to the technical field of chemical engineering. A green electrochemical synthesis mode is adopted to realize oxidative coupling of alkenyl amide, formate and aldehyde compounds through an electrochemical method, so the beta-acetamido carbonyl compound is simply, efficiently and practically prepared.The electrochemical method does not need to add additional oxidizing agents and catalysts, the method improves the raw material utilization rate of the whole process, reduces the production cost and three-waste pollution generated in the production process, is more green and environment-friendly, and has wide industrial application prospects and economic and practical values.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, especially a β - Electrochemical synthesis of acetylaminocarbonyl compounds. Background technique [0002] β -Acetamidocarbonyl compounds are widely used in the synthesis of natural products or drug molecular intermediates, and can be converted into chiral β-amino acids or chiral amines through asymmetric hydrogenation. These optically active compounds are used as proteins, polypeptides, and The structural building blocks of enzymes also play a very important role in life chemistry, so for ( β -Acetamido) carbonyl compounds have attracted widespread attention, and some unsaturated carboxylic acid esters are not only good carriers of herbicides, but also can improve herbicidal activity. Such as (Z)-2-acetylamino cinnamic acid, β -Acetamidoacrylic acid and its esters have been widely used as standard substrates to evaluate chiral hydrogenation catalysts, new chiral ligands, water-solu...

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Problems solved by technology

Using β-ketoester as raw material and ammonium acetate dehydration condensation and then acetylation to obtain multi-substituted ( β -Acetamido) carbonyl compounds (Stork G, Brizzolara A, Landesman H, et al. The enamine alkylation and acylation of carbonyl compounds[J]. Journal of the American Chemical Society, 1963, 85(2): 207-222, Kuehne M E, Garbacik T. Relative reactivities of enamines in alkylation reactions[J]. The Journal of Organic Chemistry, 1970, 35(5): 1555-1558, Hodgson D M, Bray C D, Kindon N D, et al. Synthesis and C-alkylation of hindered aldehyde enamines [J]. The Journal of organicchemistry, 2009, 74(3): 1019-1028.), but this method is difficult to control, transition metal catalyzed ( β -Arylation reaction of C-H bonds of carbonyl compounds to prepare multi-substituted ( β -Acetamido) carbonyl compounds, but the reaction conditions of this method are complicated, and there are few suitable types of substrates. Rodde et al. prepared by iron metal-catalyzed C-H bond ester carbonylation of enamides (Ding R, Zhang Q C, Xu Y H, et al . Preparation of highly substituted ( β -acylamino) acrylates via iron-catalyzed alkoxycarbonylation of N -vinylacetamides with carbazates[J]. Chemical Communications, 2014, 50(79):11661-11664.) But the catalyst is expensive to prepare, the reaction is complicated and the yield is not high. A new method of methyl 2-acetylamino-3-phenylacrylate, asymmetric catalytic technology is currently the most ideal method for the synthesis of chiral compounds, among all asymmetric catalytic reactions, olefin hydrogenation is the most studied and most promising Effective reaction, the application of asymmetric catalytic hydrogenation reaction, the conversion of prochiral substrates such as olefins, imines, ketones, etc. The product is especially suitable for the synthesis of various optically pure amino acids, such as the asymmetric oxidation of (Z)-2-acetamidocinnamic acid, and the optical purity of the product is above 99%. Therefore, dehydroamino acid compounds, such as (Z)- 2-Acetamidocinnamic acid, N-acetamidoacrylic acid and their esters have been widely used as standard substrates to evaluate chiral hydrogenation catalysts, new chiral ligands, water-soluble catalysts, metal Co, Ni and other catalysts, and immobilization Chiral catalysts, but at present, such prochiral substrates cannot be directly purchased on the market, and must be developed and prepared by themselves, resulting in difficulties in the study of asymmetric catalytic hydrogenation reactions. It is of great significance for asymmetric catalysis. This paper reports the synthesis of a new prochiral substrate of 2-acetylamino-3-arylacrylic acid containing C-C double bonds from acetylglycine and aromatic aldehydes. The raw materials are easy to obtain and the method Simple, high yield, using synthesized 2-acetamido-3-arylacrylic acid, esterification with DCC (N,N'-dicyclohexylcarbodiimide), DMAP (4-dimethylaminopyridine) As a catalyst, the post-treatment of the esterification reaction is cumbersome, which is not conducive to large-scale preparation, and the efficiency is also low. Chinese patent CN109320554 discloses a new method for the synthesis of practical acetamidoacrylate compounds. Phenyl oxazolone derivatives and organic Alcohol selectively undergoes ring-opening esterification under the catalysis of a catalyst to obtain the corresponding acetamidoacrylate compound, and the catalyst uses binaphthyl phosphate

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