Calcium carbide as a dehydrating agent for the synthesis of carbamates, glycerol carbonate, and cyclic carbonates from carbon dioxide,Green Chemistry

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Calcium carbide as a dehydrating agent for the synthesis of carbamates, glycerol carbonate, and cyclic carbonates from carbon dioxide
Green Chemistry ( IF 9.3 ) Pub Date : 2020-05-18 , DOI: 10.1039/d0gc01402h
Qiao Zhang _{1,

2,

3} , Hao-Yu Yuan _{2,

3,

4,

5} , Xiao-Tao Lin _{1,

2,

3,

4,

5} , Norihisa Fukaya _{1,

2,

3} , Tadahiro Fujitani _{1,

2,

3} , Kazuhiko Sato _{1,

2,

3} , Jun-Chul Choi _{1,

2,

3,

4,

5}

Affiliation

Carbon dioxide (CO₂) is a nontoxic and inexpensive C1 building block, which can be used for the synthesis of valuable chemicals such as aromatic carbamates from anilines and methanol (MeOH), glycerol carbonate from glycerol, and cyclic carbonates from diols. However, these reactions generate water as the byproduct and suffer from thermodynamic limits, which lead to low yields. Calcium carbide (CaC₂) is a renewable chemical, which can be recycled from calcium that is abundant in the Earth's crust. Furthermore, CaC₂ rapidly reacts with water. In this work, we used CaC₂ as a dehydrating agent for the direct synthesis of carbamates (including polyurethane precursors) from amines, CO₂, and MeOH. All reagents were commercially available. In addition, CaC₂ was employed for the synthesis of glycerol carbonate from glycerol and CO₂ with a zinc catalyst and N-donor ligand. A similar protocol was applied to synthesize cyclic carbonates from diols and CO₂.

中文翻译：

碳化钙作为脱水剂，用于从二氧化碳合成氨基甲酸酯，碳酸甘油酯和环状碳酸酯

二氧化碳（CO ₂）是一种无毒且廉价的C1结构单元，可用于合成有价值的化学物质，例如由苯胺和甲醇（MeOH）合成的芳族氨基甲酸酯，由甘油合成的碳酸甘油酯和由二醇合成的环状碳酸酯。然而，这些反应产生水作为副产物并且受热力学极限的影响，这导致低产率。电石（CaC ₂）是一种可再生的化学物质，可以从地壳中丰富的钙中回收利用。此外，CaC ₂与水迅速反应。在这项工作中，我们使用CaC ₂作为脱水剂，由胺，CO ₂直接合成氨基甲酸酯（包括聚氨酯前体）和MeOH。所有试剂都是可商购的。另外，使用CaC ₂，利用锌催化剂和N-给体配体，由甘油和CO ₂合成碳酸甘油酯。将类似的方案应用于从二醇和CO ₂合成环状碳酸酯。

更新日期：2020-07-06

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