Method for preparing tetronic acid by cyclization of propargyl alcohol and carbon dioxide

A technology of carbon dioxide and propargyl alcohol, applied in the field of chemistry, can solve the problems of harsh reaction conditions, improved reaction selectivity, difficult preservation and the like, and achieves the effect of high yield

Active Publication Date: 2021-07-02
SICHUAN UNIV
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Problems solved by technology

Although various catalysts for this reaction have developed rapidly in recent years, and there have been many examples of organic catalysts replacing metal catalysts, there is still no breakthrough in the field of reaction between aryl propargyl alcohol and carbon dioxide, which can only be carried out under pressure. And there are still catalyst stability and reaction selectivity problems (carbene instability and reaction selectivity need to be improved: Yoshihito Kayaki, Masafumi Yamamoto, and TakaoIkariya, Angew.Chem., Int.Ed.2009,48,4194.Yan -Bo Wang, Yi-Ming Wang, Wen-Zhen Zhang, and Xiao-Bing Lu, J.Am.Chem.Soc.2013, 135, 11996; Yan-Bo Wang, Dong-ShengSun, Hui Zhou, Wen-Zhen Zhang and Xiao-Bing Lu, Green Chem., 2014, 16, 2266; Alkyl azaene-carbon dioxide adduct catalyst: Hui Zhou, Guo-Xu Wang, and Xiao-Bing Lu, Asian Journal of Organic Chemistry, 2017, 6, 1264; Silver carbene complexes supported on styrene (0 yield with aryl propargyl alcohol as substrate): Xiaodong Tang, Chaorong Qi, Haitao He, Huanfeng Jiang, Yanwei Ren, and Gaoqing Yuan, Adv .Synth.Catal.2013,355,2019; Ionic liquids (high pressure and ionic liquids are easy to absorb water and difficult to store): Jikuan Qiu, Yuling Zhao, Zhiyong Li, Huiyong Wang, Maohong Fan, and Jianji Wang, ChemSusChem2016,9,1)
Although aryl propargyl alcohol can react under atmospheric pressure, available yield is only 35% product (K.Uemura, T.Kawaguchi, H.Takayama, A.Nakamura, Y.Inoue, Journal of Molecular Catalysis A:Chemical ,1999,139 1)
In 2017, the problem of pressurized reaction conditions and low reaction yield of aryl propargyl alcohol was effectively improved, and the yield of phenyl-substituted alkenyl cyclic carbonate product could reach 50%, but the ionic liquid conditions used in the reaction Not conducive to large-scale industrial production (Yunyan Wu, Yanfei Zhao, Ruipeng Li, Bo Yu, Yu Chen, Xinwei Liu, Cailing Wu, Xiaoying Luo, and Zhimin Liu, ACS Catal.2017, 7, 6251)
Although the system has made a breakthrough compared with the reaction conditions of previous work, it still needs the participation of silver (Ye Yuan, YuXie, Cheng Zeng, Dandan Song, Somboon, Chaemchuen, Cheng Chen, Francis Verpoort, Catal.Sci.Technol .,2017,7,2935)
[0006] In summary, the cyclization reaction of propargyl alcohol and carbon dioxide still has challenges such as strong catalyst dependence, harsh reaction conditions, and poor applicability of aryl substrates.
[0007] Because of its unique properties, tetronic acid is widely used in the fields of medicine, pesticides, polymer materials and dyes, so chemists have also developed many methods for synthesizing tetronic acid, but there are still cumbersome routes or active starting materials. , or harsh reaction conditions, such as: starting from corrosive aryl acetyl chloride, two-step synthesis of tetronic acid, and the second step needs to be carried out under reflux conditions (Jin-Hao Zhao, Zong-Cheng Wang, Ming-Hua Ji, Jing-Li Cheng, Guo-Nian Zhu and Chuan-Ming Yu, Pest Manag Sci 2012,68,1); Another example is the generation of 3-diazofuran-2,4-dione by C-H activation of aromatic hydrocarbons Cross-coupling to obtain tetronic acid requires the use of noble metal Rh; and if some reactions require and dangerous reagent butyllithium is the starting material (Liu Shaohua, Wang Zhenyu, Wang Jinjin, Wang Jinhua, Shi Hui, Guo Yayun, Fine and Specialty Chemicals, 2015 ,23,36)

Method used

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  • Method for preparing tetronic acid by cyclization of propargyl alcohol and carbon dioxide
  • Method for preparing tetronic acid by cyclization of propargyl alcohol and carbon dioxide
  • Method for preparing tetronic acid by cyclization of propargyl alcohol and carbon dioxide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Example 1 Synthesis of 5,5-dimethyl-4-hydroxyl-3-(4-cyanophenyl)-2(5H)-furanone (compound 2a)

[0039]

[0040] Accurately measure 4-(4-cyano-phenyl)-2-methyl-3-butyn-2-ol 1a (74.1 mg, 0.4 mmol) into the sealed tube, and weigh K under nitrogen 2 CO 3 (442.3 mg, 3.2 mmol), 2 mL of acetonitrile was added, and carbon dioxide was introduced. Under normal pressure, react at 25°C for 8 hours, cool to room temperature, quench with 2M hydrochloric acid solution, extract with dichloromethane, concentrate the organic phase, and perform column chromatography to obtain 84.4 mg (0.368 mmol) of a white solid product with a yield of 92%. .

[0041] 1 H NMR (400MHz, DMSO-d 6 ) δ8.39~8.33 (m, 2H), 7.68~7.56 (m, 2H), 1.35 (s, 6H).

Embodiment 2

[0042] Example 2 Synthesis of 5-methyl-5-ethyl-4-hydroxyl-3-(4-cyanophenyl)-2(5H)-furanone (compound 2b)

[0043]

[0044] Accurately measure 4-(4-cyano-phenyl)-3-methyl-4-pentyn-3-ol 1b (79.7mg, 0.4mmol) into the sealed tube, weigh DBU (487.2mg, 3.2mmol), add 3mL DMF (N,N-dimethylformamide), and pass through carbon dioxide. Under normal pressure, react at 25°C for 8 hours, cool to room temperature, quench with 2M hydrochloric acid solution, extract with dichloromethane, concentrate the organic phase, and perform column chromatography to obtain 82.7mg (0.340mmol) of a white solid product with a yield of 85% .

[0045] 1 H NMR (400MHz, DMSO-d 6 )δ8.47(d, J=8.4Hz, 2H), 7.49~7.47(m, 2H), 1.56(ddq, J=28.4, 14.3, 7.2Hz, 2H), 1.19(s, 3H), 0.71(t , J=7.4Hz, 3H).

Embodiment 3

[0046] Example 3 Synthesis of 5,5-diethyl-4-hydroxyl-3-(4-cyanophenyl)-2(5H)-furanone (compound 2c)

[0047]

[0048] Accurately measure 4-(4-cyano-phenyl)-3-methyl-4-pentyn-3-ol 1c (85.3 mg, 0.4 mmol) into the sealed tube, weigh CsF (486.1 mg, 3.2 mmol), 5 mL of DMI (1,3-dimethylimidazolidinone) was added, and carbon dioxide was introduced. Under normal pressure, react at 25°C for 8 hours, cool to room temperature, quench with 2M hydrochloric acid solution, extract with dichloromethane, concentrate the organic phase, and perform column chromatography to obtain 77.2 mg (0.300 mmol) of a white solid product with a yield of 75%. .

[0049] 1 H NMR (400MHz, DMSO-d6) δ8.18 (d, J = 8.2Hz, 2H), 7.79 (d, J = 8.2Hz, 2H), 1.86 (dq, J = 14.9, 7.2Hz, 4H), 0.73 (t, J=7.3Hz, 6H).

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Abstract

The invention belongs to the field of biochemistry, and mainly relates to a method for preparing tetronic acid through cycloenolization of propargyl alcohol and carbon dioxide. The invention provides a method for preparing tetronic acid through cycloenolization of propargyl alcohol and carbon dioxide. The method simply uses alkali, solvent and normal pressure to react propargyl alcohol with carbon dioxide to obtain tetronic acid. The method provided by the invention can greatly increase the yield, and can realize gram-level scale, and has the possibility of realizing industrialization. Therefore, the new method system and new strategy provided by the present invention have great development prospects. This is also the first realization of the synthesis of tetronic acid starting from propargyl alcohol and carbon dioxide.

Description

technical field [0001] The invention belongs to the field of chemistry, and in particular relates to a method for preparing tetronic acid through cycloenolization of propargyl alcohol and carbon dioxide. Background technique [0002] The greenhouse effect caused by carbon dioxide has become a global problem. However, in the eyes of chemists, carbon dioxide is a source of C1 with huge reserves. If people can use carbon dioxide as raw material to produce various high value-added chemicals, it will not only effectively reduce the greenhouse effect caused by carbon dioxide, but also reduce the impact on Reliance on traditional fossil fuels. However, compared with the more active carbon monoxide, carbon dioxide molecules are very stable, and the activation conditions are usually harsh. How to activate carbon dioxide under mild conditions has always been a huge challenge for the resource utilization of carbon dioxide. [0003] Among the various strategies for resource utilizatio...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D307/60C07D307/94C07D405/04
CPCC07D307/60C07D307/94C07D405/04
Inventor 余达刚李静申国周文俊张晓波曹光梅张振叶剑衡廖黎丽
Owner SICHUAN UNIV
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