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Method for preparing propiolic acid and derivatives thereof under mild condition

A technology of propiolic acid and terminal alkyne, which is applied in the field of preparing propiolic acid and its derivatives, can solve the problems of restricting large-scale use, and achieve the effects of avoiding the use of precious metals, mild reaction conditions, and strong industrial application value

Active Publication Date: 2018-08-21
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above-mentioned catalytic systems usually require the use of expensive metals and organic ligands, which limits their large-scale industrial use.

Method used

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  • Method for preparing propiolic acid and derivatives thereof under mild condition
  • Method for preparing propiolic acid and derivatives thereof under mild condition
  • Method for preparing propiolic acid and derivatives thereof under mild condition

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment 1, phenylacetylene and CO 2 Carboxylation to phenylpropiolic acid

[0028] In the glove box, into a 10 ml Schlenk bottle, add phenylacetylene (1mol), HSi(OEt) 2 Me(5mol) and KO t Bu (1.5mol) with CO 2 Displace the air; connect the Schlenk bottle to CO 2 Air bag, stirred at 40°C for 2 hours. After the reaction is over, add 30mL H 2 O to dilute the reaction solution with CH 2 Cl 2 (3 x 10 mL) extraction. The aqueous layer was acidified by adding HCl (6M) solution, and finally extracted with diethyl ether (5×20 mL). The obtained organic layer was dried over anhydrous magnesium sulfate, and then vacuum rotary evaporated to obtain the pure product with an isolated yield of 98%.

[0029] reaction product 1 H and 13 C nuclear magnetic spectrum to determine its structure:

[0030] 1 H NMR (400MHz, DMSO) δ 7.68-7.62 (m, 2H), 7.55 (d, J=7.4Hz, 1H), 7.49 (t, J=7.4Hz, 2H).

[0031] 13 C NMR (101 MHz, DMSO) δ 154.81, 133.07, 131.36, 129.50, 119.53, 119.51, 8...

Embodiment 2

[0033] Embodiment 2, phenylacetylene and CO 2 Carboxylation to phenylpropiolic acid

[0034] In the glove box, add phenylacetylene (1mol), Et 3 SiH(5mol) and KO t Bu (1.5mol) with CO 2 Displace the air; connect the Schlenk bottle to CO 2 Air bag, stirred at 40°C for 2 hours. After the reaction is over, add 30mL H 2 O to dilute the reaction solution with CH 2 Cl 2 (3 x 10 mL) extraction. The aqueous layer was acidified by adding HCl (6M) solution, and finally extracted with diethyl ether (5×20 mL). The obtained organic layer was dried over anhydrous magnesium sulfate, and then vacuum rotary evaporated to obtain pure product with an isolated yield of 40%.

Embodiment 3

[0035] Embodiment 3, phenylacetylene and CO 2 Carboxylation to phenylpropiolic acid

[0036]In the glove box, into a 10 ml Schlenk bottle, add phenylacetylene (1mol), (EtO) 3 SiH(5mol) and KO t Bu (1.5mol) with CO 2 Displace the air; connect the Schlenk bottle to CO 2 Air bag, stirred at 40°C for 2 hours. After the reaction is over, add 30mL H 2 O to dilute the reaction solution with CH 2 Cl 2 (3 x 10 mL) extraction. The aqueous layer was acidified by adding HCl (6M) solution, and finally extracted with diethyl ether (5×20 mL). The obtained organic layer was dried over anhydrous magnesium sulfate, and then vacuum rotary evaporated to obtain the pure product with an isolated yield of 86%.

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Abstract

The invention provides a novel method for preparing propiolic acid compounds through a domino reaction. The method comprises a step of subjecting terminal alkyne compounds, hydrosilane and CO2 to thedomino reaction under the catalysis action of Lewis base so as to obtain propiolic acid compounds. According to the invention, common Lewis base is used as a promoter, and corresponding propiolic acidcompounds containing different function groups can be efficiently produced through a reaction of the terminal alkyne compounds with hydrosilane and normal-pressure CO2 under a mild condition (a temperature of 40 DEG D). According to the method, CO2 is used as a raw material; the cheap Lewis base is used as the promoter; usage of precious metals is avoided; the domino reaction is employed; purification and separation of intermediates are not needed; and reaction conditions are mild. Thus, the method is an efficient cheap green synthetic method and has good industrial application value.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a method for preparing propiolic acid and its derivatives under mild conditions. Background technique [0002] Propiolic acid compounds are a very important class of organic intermediates, which are widely used in organic synthesis and are often used to prepare functional materials (L.Z.Zhang, Z.J.Hang, Z.Q.Liu, Angew.Chem.Int.Ed.2015, 55, 236-239). Therefore, it is of great significance to develop efficient methods for the synthesis of propiolic acid compounds. [0003] Terminal alkynes and CO 2 The carboxylation reaction is an atom-economical method for the synthesis of propiolic acid compounds. Currently the most commonly used process is the use of aryl alkynyl lithium reagents or magnesium reagents with CO 2 reaction (Polyzos, A.; O'Brien, M.; Petersen, T.P.; Baxendale, I.R.; Ley, S.V. Angew. Chem. Int. Ed. 2011, 50, 1190-1193; ), however, since the process requires prior...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C57/42C07C59/64C07C57/60C07C59/48C07C57/26C07C51/15C07C201/12C07C205/56C07C253/30C07C255/57C07C67/313C07C69/76C07D333/24
CPCC07C51/15C07C67/313C07C201/12C07C253/30C07D333/24C07C57/42C07C59/64C07C57/60C07C59/48C07C57/26C07C205/56C07C255/57C07C69/76
Inventor 于博刘志敏赵燕飞杨珍珍张宏晔杨冠英
Owner INST OF CHEM CHINESE ACAD OF SCI
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