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Synthesis of 1,4‐Cyclohexanedimethanol, 1,4‐Cyclohexanedicarboxylic Acid and 1,2‐Cyclohexanedicarboxylates from Formaldehyde, Crotonaldehyde and Acrylate/Fumarate
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-05-08 , DOI: 10.1002/anie.201801287
Yancheng Hu 1 , Zhitong Zhao 1, 2, 3 , Yanting Liu 1 , Guangyi Li 1 , Aiqin Wang 1 , Yu Cong 1 , Tao Zhang 1 , Feng Wang 1 , Ning Li 1
Affiliation  

Valuable polyester monomers and plasticizers—1,4‐cyclohexanedimethanol (CHDM), 1,4‐cyclohexanedicarboxylic acid (CHDA), and 1,2‐cyclohexanedicarboxylates—have been prepared by a new strategy. The synthetic processes involve a proline‐catalyzed formal [3+1+2] cycloaddition of formaldehyde, crotonaldehyde, and acrylate (or fumarate). CHDM is produced after a subsequent hydrogenation step over a commercially available Cu/Zn/Al catalyst and a one‐pot hydrogenation/oxidation/hydrolysis process yields CHDA, whereas 1,2‐cyclohexanedicarboxylate is obtained by a Pd/C‐catalyzed tandem decarbonylation/hydrogenation step.

中文翻译:

由甲醛,巴豆醛和丙烯酸酯/富马酸酯合成1,4-环己烷二甲醇,1,4-环己烷二羧酸和1,2-环己烷二羧酸

通过一种新策略可以制备出有价值的聚酯单体和增塑剂-1,4-环己烷二甲醇(CHDM),1,4-环己烷二羧酸(CHDA)和1,2-环己烷二羧酸酯。合成过程涉及甲醛,巴豆醛和丙烯酸酯(或富马酸酯)的脯氨酸催化的正式[3 + 1 + 2]环加成反应。CHDM是在随后的商业化Cu / Zn / Al催化剂上进行加氢步骤后产生的,单锅加氢/氧化/水解过程可生成CHDA,而1,2-环己烷二羧酸盐则是通过Pd / C催化的串联脱羰/氢化步骤。
更新日期:2018-05-08
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