Using Sodium Hydride and Potassium Carbonate as Bases in Synthesis of Substituted 2-Amino-4-aryl-7-propargyloxy-4H-chromene-3-carbonitriles

Author(s): Nguyen D. Thanh*, Do S. Hai, Vu T.N. Bich, Pham T.T. Hien, Nguyen T.K. Duyen, Nguyen T. Mai, Tran T. Dung, Hoang T.K. Van, Vu N. Toan, Duong N. Toan, Le H. Dang.

Journal Name: Current Organic Synthesis

Volume 16 , Issue 3 , 2019

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Graphical Abstract:


Aims and Objective: 1-Alkynes are the important precursors for the CuAAC click chemistry. The hybrid of 1,2,3-triazole ring to the chromene ring and sugar moiety could bring some remarkable biological properties. Propargyl derivatives are usually used in the click chemistry. This article reported the synthesis of 2-amino-4-aryl-7-propargyloxy-4-aryl-4H-chromene-3-carbonitriles using propargyl bromide as alkylation agent and the use of potassium carbonate and sodium hydride as bases in the conversion of 2-amino-4-aryl-7- hydroxy-4-aryl-4H-chromene-3-carbonitriles into corresponding propargyl ethers in Williamson’s ether synthesis.

Materials and Methods: The use of CTAB for the synthesis of benzylidene malononitriles and anhydrous potassium carbonate as a catalyst in absolute ethanol in the synthesis of 2-amino-7-hydroxy-4H-chromene-3- carbonitriles is an efficient and simple synthetic method. Propargyl ether compounds of these 4H-chromene-3- carbonitriles were obtained from the alkylation reaction by propargyl bromide. Two procedures were applied: K2CO3 as a base in acetone solvent (Procedure A) and NaH as a base in DMF solvent (Procedure B). The single-crystal X-ray structure of propargyl ether 5e has been studied.

Results: The use of K2CO3 and NaH as bases in the Williamson’s ether synthesis from 2-amino-7-hydroxy-4Hchromene- 3-carbonitriles showed that Procedure B was the better route and gave ethers in the higher yields. 2- Amino-4-aryl-7-propargyloxy-4-aryl-4H-chromene-3-carbonitriles were obtained from corresponding 7- hydroxy-4H-chromene-3-carbonitriles. Yields of ethers 5a-i were 70−89% and 80−96%, respectively depending on the used procedures.

Conclusion: The described methods are simple, clean and environmentally friendly alternatives for the preparation of 2-amino-4-aryl-7-hydroxy-4H-chromene-3-carbonitriles. The conditions for the transformation of these compounds into propargyl ethers include dried DMF as a solvent, NaH as a base and reaction time of 2 h at the room temperature. A series of 2-amino-4-aryl-7-hydroxy-4-aryl-4H-chromene-3-carbonitriles were obtained based on investigated reaction condition.

Keywords: 4H-Chromene, multi-component reaction, propargyl ether, potassium carbonate, sodium hydride, Williamson’s ether synthesis.

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Article Details

Year: 2019
Page: [423 - 430]
Pages: 8
DOI: 10.2174/1570179416666190104124652
Price: $58

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