Revisit of Thiele’s acid synthesis from CO2 and cyclopentadiene and use for TCD-amine preparation with all-endo specific stereochemistry

IF 8.4 2区工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of CO2 Utilization Pub Date : 2025-07-24 DOI:10.1016/j.jcou.2025.103177

Fu-En Szu , Chen-Wei Yang , Yi-Zhen Li , Yin-Yin Yu , Chun-I Huang , Jia-Hong Chen , Jui-Hsiung Huang , Man-kit Leung

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引用次数: 0

Abstract

This study provides a mild procedure using CO₂, cyclopentadiene, and sodium tert-butoxide for Thiele’s acid in good yields and high purity. The product distribution of Thiele's acid and other isomeric forms can be tuned by utilizing different metal cations. Among the bases we have tried, sodium tert-butoxide can selectively provide Thiele’s acid as the major product in 72 % isolated yield, along with an endo, endo-pentacyclopentadecadienetricarboxylic acid, denoted as PCPD-triacid as the side product. Thiele’s acid and PCPD-triacid can be hydrogenated in aqueous alkaline solution to give the corresponding all-endo tetrahydro-derivatives, denoted as THDCPD-diacid and THPCPD-triacid. Functional group transformation of the carboxylic acids to alcohols and amines, such as THDCPD-diol and THDCPD-diamine, has been successfully demonstrated. Their chemical structures and stereochemistry are confirmed by X-ray crystallographic analysis. THDCPD-diamine is stereochemically complementary to the commercially available TCD-diamine with high purity and can serve as versatile polymer monomers or cross-linking agents, significantly expanding their potential for use in various applications.

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以CO2和环戊二烯为原料合成Thiele酸及其在全端特异性立体化学制备tcd胺中的应用

本研究提供了一种用CO2、环戊二烯和叔丁二氧化钠制备Thiele酸的温和工艺，收率高，纯度高。蒂勒酸和其他异构体的产物分布可以通过利用不同的金属阳离子来调节。在我们所尝试的碱中，叔丁二氧化钠可以选择性地提供Thiele酸作为主要产物，分离收率为72% %，同时还可以提供内端，内五环五十六烯二羧酸，标记为pcpd -三酸作为副产物。Thiele 's酸和pcpd -三酸可在碱性水溶液中加氢生成相应的全端四氢衍生物，记为thdcpd -二酸和thpcpd -三酸。羧酸的官能团转化为醇和胺，如thdcpd -二醇和thdcpd -二胺，已被成功证明。它们的化学结构和立体化学被x射线晶体学分析证实。thdcpd -二胺在立体化学上与市售的tcd -二胺互补，具有高纯度，可作为多用途聚合物单体或交联剂，极大地扩展了其在各种应用中的潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of CO2 Utilization CHEMISTRY, MULTIDISCIPLINARY-ENGINEERING, CHEMICAL

CiteScore

13.90

自引率

10.40%

发文量

406

审稿时长

2.8 months

期刊介绍： The Journal of CO2 Utilization offers a single, multi-disciplinary, scholarly platform for the exchange of novel research in the field of CO2 re-use for scientists and engineers in chemicals, fuels and materials. The emphasis is on the dissemination of leading-edge research from basic science to the development of new processes, technologies and applications. The Journal of CO2 Utilization publishes original peer-reviewed research papers, reviews, and short communications, including experimental and theoretical work, and analytical models and simulations.