Preparation method of propiolic acid compounds

Abstract

The invention relates to CO2 activation and conversion and related chemical technical fields, and specifically relates to a synthesis method of propiolic acid compounds. The method is characterized in that in the presence of an added additive and alkalis, terminal alkynes directly react with CO2 to generate propiolic acid compounds. The proper terminal alkyne substrate may be phenyl acetylene, substituted phenyl acetylene, heterocyclic aryl alkynes, or aliphatic terminal alkynes. Compared with the prior art, the invention mainly provides a novel and simple reaction system. According to the preparation method, potassium carbonate is taken as the alkali, quaternary ammonium salts are taken as the additive, and acetonitrile, which is convenient for the post treatment, is taken as the solvent. The preparation method is reported for the first time. The reaction system does not need any transition metal catalyst; the experiment operation is simple; the raw materials are cheap and easily available, and the preparation method is environment-friendly and generates great application value, social benefits, and economic benefits.

Description

technical field [0001] The present invention relates to CO 2 The field of activation transformation and related chemical technology relates to a preparation method of propiolic acid compounds. Background technique [0002] Carbon dioxide is an abundant, cheap and renewable C 1 resources, and the research on their activation and conversion into high value-added fine chemicals has attracted widespread attention. In the past few decades, many methods for carbon dioxide fixation and conversion have been reported [see: (a) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365. (b) Q. Liu; L. Wu; R. Jackstell; M. Beller, Nat. Commun. 2015, 6, 5933.]. Propiolate compounds are important synthetic intermediates and are widely used in the synthesis of fine chemicals and pharmaceutical molecules. Therefore, the synthesis of propiolic acid compounds has been widely concerned. In the prior art, the method for synthesizing propiolic acid compounds is mainly the oxidative c...

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Problems solved by technology

In the prior art, the method for synthesizing propiolic acid compounds is mainly the oxidative carboxylation reaction of alkynes, using formaldehyde or carbon monoxide as the carboxylation reagent, but this method has problems such as high toxicity of CO

Recently, it has been reported in the literature that the use of transition metal catalysis or cesium carbonate to promote CO 2 React with terminal alkynes to prepare propiolic acid compounds, but there are many problems such as expensive transition metal catalysts, bulky ligands, difficult synthesis, and difficult post-treatment of high-boiling solvents [see (a) Dingyi Yu; Yugen Zhang, PNAS, 2010 ,47,20189.(b)HaoCheng;Bei Zhao;Yingming Yao;Chengrong Lu.Green Chem.,2015,17,1675;(c)ManojTrivedi;a Abhinav Kumarb;Nigam P.Rath.Dalton Trans.,2015,44 ,20874;(d)SeungHyo Kim;Kwang Hee Kim;Soon Hyeok Hong.Angew.Chem.Int.Ed.2014,53,771;(e)Xiao-Huan Liu;Jian-Gong Ma;Zheng Niu;Guang-Ming Yang; PengCheng.Angew.Chem.Int.Ed.2015,54,988]

It has also been reported that carbon dioxide and terminal alkynes are used as raw materials to generate propiolic acid compounds in a metal-free catalytic system, but the used base TBD and cesium carbonate are relatively expensive, and the solvents such as DMF used are difficult to handle [see document (a) Yu Dingyi, Zhang Yugen, Green Chem., 2011, 13, 1275; (b) X.Wang, Y.N.Lim, C.Lee, H.-Y.Jang, B.Y.Lee, Eur.J.Org.Chem.2013, 1867]

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