Empa, Swiss Federal Laboratories for Materials Science and Technology,Laboratory for Advanced Analytical Technologies, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland.
Empa, Swiss Federal Laboratories for Materials Science and Technology,Laboratory for Advanced Analytical Technologies, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland; ZHAW, Zurich University of Applied Sciences, Institute of Chemistry and Biological Chemistry, Reidbach, CH-8820, Wädenswil, Switzerland.
Chemosphere. 2020 Sep;255:126959. doi: 10.1016/j.chemosphere.2020.126959. Epub 2020 May 1.
The photolytic chlorination of n-alkanes in presence of sulfuryl chloride (SOCl) was explored to produce new standard materials. Five mixtures of chlorinated tetradecanes were synthesized with chlorination degrees (m) varying from 43.7% to 59.4% (m/m) based on elemental analysis. Chlorine-enhanced negative chemical ionization mass spectrometry (CE-NCI-MS) forcing the formation of chloride-adduct ions [M+Cl] was applied to characterize these materials which all contained tetra-to deca-chlorinated paraffins. Deconvolution of respective mass spectra revealed the presence of chlorinated olefins (COs). CO levels were highest in materials, which were exposed longest. All synthesized materials also contained two classes of polar impurities, tentatively assigned as sulfite- and sulfate-diesters with molecular formulas of CHOSCl (x = 1-4) and CHOSCl (x = 3-6), respectively. MS data were in accordance with the proposed structures but further work is needed to deduce their constitutions. These compounds are thermolabile and were not detected with GC-MS methods. We could remove these sulfur-containing impurities from the CPs with normal-phase liquid chromatography. In conclusion, single-chain CP materials were synthesized via chlorination of n-alkanes with sulfuryl chloride, but these materials contained reactive side products which should be removed to gain non-reactive and stable CP materials suitable as standards and for fate and toxicity studies.
探索了在氯化亚砜 (SOCl) 存在下将正烷烃光氯化以生产新的标准物质。根据元素分析，合成了五种氯化十四烷混合物，其氯化度 (m) 从 43.7% 到 59.4%（m/m）不等。应用增强型负化学电离质谱（CE-NCI-MS）强制形成氯加合物离子 [M+Cl] 来表征这些材料，这些材料均含有四氯至十氯代石蜡。各自质谱的解卷积揭示了氯化烯烃 (COs) 的存在。在暴露时间最长的材料中，CO 水平最高。所有合成的材料还含有两类极性杂质，暂定分别为亚硫酸酯和硫酸酯二酯，其分子式分别为 CHOSCl (x = 1-4) 和 CHOSCl (x = 3-6)。MS 数据与提出的结构一致，但需要进一步工作来推断它们的组成。这些化合物热不稳定，不能用 GC-MS 方法检测到。我们可以用正相液相色谱法从 CPs 中去除这些含硫杂质。总之，通过氯化亚砜将正烷烃氯化合成了单链 CP 材料，但这些材料含有反应性副产物，应去除这些副产物，以获得非反应性和稳定的 CP 材料，用作标准物质以及用于研究其归趋和毒性。
