多氯联苯标样的高效制备与GC表征研究进展

Progress in Efficient Preparation and GC Characterization of Polychlorinated Biphenyl Reference Standards

摘要: 针对我国现行环境标准中多氯联苯(PCBs)单体覆盖严重不足的现状，本文系统综述了基于“氧气辅助无配体Pd/C催化Suzuki反应”的绿色合成策略及其在PCBs标准样品高效制备中的应用进展。文章首先梳理了从传统乌尔曼反应到Suzuki偶联的PCBs单体制备发展路径，指出现行主流方法在成本、效率及环境友好性方面的局限。进而重点评述了以非均相Pd/C催化剂、乙醇/水绿色溶剂及敞口反应体系为核心的绿色Suzuki方案，其在温和条件下可实现多种PCBs单体的高效、高选择性合成，且催化剂可循环使用，显著降低了经济与环境成本。此外，本文还探讨了气相色谱–质谱联用技术在合成产物纯度验证与环境标准符合性评价中的关键作用。最后，展望了该绿色路线在合成高氯代大位阻单体及实现连续流规模化制备方面的挑战与前景，指出该体系有望为我国新污染物治理提供自主可控、覆盖全面的标准物质支撑。

Abstract: Addressing the severe inadequacy of monomer coverage for polychlorinated biphenyls (PCBs) in China’s current environmental standards, this paper systematically reviews the green synthetic strategy based on “oxygen-assisted ligand-free Pd/C-catalyzed Suzuki reaction” and its application progress in the efficient preparation of PCB standard samples. The paper first traces the developmental trajectory of PCB monomer synthesis from the traditional Ullmann reaction to Suzuki coupling, highlighting the limitations of current mainstream methods in terms of cost, efficiency, and environmental friendliness. It then focuses on evaluating the green Suzuki approach, characterized by heterogeneous Pd/C catalysts, ethanol/water green solvents, and open-system reactions. This method enables the efficient and highly selective synthesis of various PCB monomers under mild conditions, with recyclable catalysts that significantly reduce economic and environmental costs. Additionally, this paper explores the critical role of gas chromatography-mass spectrometry (GC-MS) in verifying the purity of synthetic products and evaluating compliance with environmental standards. Finally, it outlines the challenges and prospects of this green approach for synthesizing highly chlorinated, sterically hindered monomers and achieving continuous-flow, large-scale production. It concludes that this system holds promise for providing China with independently controlled, comprehensive standard material support for addressing emerging pollutants.