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Progress in Chemistry 2022, Vol. 34 Issue (6): 1431-1439 DOI: 10.7536/PC210909 Previous Articles   Next Articles

• Review •

Catalytic Synthesis of N,N-Dimethylformamide from Carbon Dioxide and Dimethylamine

Yajuan Wu1(), Jingwen Luo1, Yongji Huang2   

  1. 1 Key Laboratory of General Chemistry of the National Ethnic Affairs Commission, School of Chemistry and Environment, Southwest Minzu University, Chengdu 610041, China
    2 State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences,Lanzhou 730000, China
  • Received: Revised: Online: Published:
  • Contact: Yajuan Wu
  • Supported by:
    National Natural Science Foundation of China(22002122); Fundamental Research Funds for the Central Universities, Southwest Minzu University(2020NQN08)
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Global warming and the energy crisis are posing increasingly severe risks for the economy, ecosystems and human health. As one kind of dominant greenhouse gas, carbon dioxide (CO2) contributes most to global warming, while it is also considered as an abundant, nontoxic, and renewable C1 source. Thus far, transforming CO2 into high value-added chemicals through modern technologies has attracted significant attention owing to its unique advantages. It can not only alleviate human reliance on fossil resources, but also effectively weaken the greenhouse effect. It is of great help to achieve China’s “dual-carbon” goal of “carbon peak and carbon neutrality”. N,N-Dimethylformamide (DMF), an extremely versatile solvent and important chemical intermediate, can be synthesized by using CO2 and dimethylamine as raw materials over different catalysts. Therefore, the development of efficient catalytic systems is crucial for the transformation of CO2 into high value-added products. This article reviews the current status and progress in the synthesis of DMF with CO2 and dimethylamine with respect to reducing agents, catalytic systems as well as the reaction mechanisms of these different catalytic systems. Furthermore, we conclude the frontiers and future prospects of the catalytic synthesis of DMF from CO2 and dimethylamine, providing readers a snapshot of this field.

Contents

1 Introduction

2 H2 as reducing agent

2.1 Noble catalytic system

2.2 Non-noble catalytic system

3 Other reducing agent

3.1 Hydrosilanes as reducing agent

3.2 Boranes as reducing agent

3.3 Ammonium salts as reducing agent

4 Conclusion and outlook

Key words: CO2, dimethylamine, N,N-dimethylformamide, catalytic system
Fig. 1 Catalytic synthesis of DMF with dimethylamine and CO2/ H 2 [7]
Fig. 2 The reaction mechanism of DMF synthesis catalyzed by (PPh3)3RhCl[9]
Fig. 3 Reaction mechanism of Ru-catalyzed synthesis of DMF[12]
Fig. 4 Ru pincer catalyze formylation of dimethylamine with CO2/ H 2 [18]
Fig. 5 Mechanism for DMF synthesis catalyzed by Ru-Macho[23]
Fig. 6 Concept of the two-step process for the synthesis of DMF[24]
Fig. 7 Co pincer catalyze formylation of dimethylamine with CO2/ H 2 [25]
Fig. 8 Co pincer catalyze formylation of amine with CO2/ H 2 [30]
Fig. 9 Ni(Ⅱ)-catalyzed DMF synthesis from CO2/ H 2 [31]
Fig. 10 Formylation of dimethylamine catalyzed by PS-PEG-bound Ru complexes[37]
Fig. 11 Synthesis of Ru@PP-POP catalysts[38]
Fig. 12 Structure of NHCs-Ir and POMPs-NHC-Ir[47]. Copyright 2021, Wiley-VCH
Fig. 13 Structure of FeNi3/KCC-1/APTPOSS/TCT/PVA/Cu(Ⅱ) MNPs[52]
Fig. 14 Reduction of CO2 by silane as hydrogen source[56,57]
Fig. 15 Proposed reaction mechanism for dialkyl formamide and HCOOH generation by CO2 reduction[67]
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