Preparation method of propiolic acid compounds

Abstract

The invention belongs to the technical fields of carbon dioxide activation and conversion and related chemistry, and discloses a preparation method of propiolic acid compounds. The preparation method comprises the following steps: (1) adding a copper catalyst, an additive, an alkali, and solid terminal alkynes into a reactor, adding an organic solvent under the protection of nitrogen gas, and filling CO2 into the reactor; or adding a copper catalyst, an additive, and an alkali into a reactor, adding an organic solvent and liquid terminal alkynes, and filling CO2 into the reactor; (2) sealing the reactor, and placing the reactor in an oil bath to carry out reactions; and (3) after reactions, opening a valve of the reactor to slowly release residual gas in the reactor, transferring the reaction liquid to a one-mouth bottle, carrying out concentration, diluting the concentrate by deionized water, adding n-hexane to carry out extraction, adding hydrochloric acid to carry out acidification, adding diethyl ether to carry out extraction, collecting the organic phase, washing the organic phase by a saturated saline solution, drying the organic phase by anhydrous sodium sulfate, filtering, and removing the solvent in vacuum to obtain the target material. The preparation method has the advantages of low reaction cost, simple experiment operation, mild reaction conditions, and easiness for industrialization.

Description

technical field [0001] The invention relates to a preparation method of propiolic acid compounds, belonging to the field of carbon dioxide activation transformation and related chemical technology. Background technique [0002] Carbon dioxide is an abundant, cheap and renewable carbon resource, and the research on its activation and transformation 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 oxid...

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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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