Tretyakov K V, Babushok V I
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia.
J Chromatogr A. 2009 Jan 30;1216(5):882-4. doi: 10.1016/j.chroma.2008.11.087. Epub 2008 Dec 6.
The retention indices of methyl and trimethylsilyl esters of octadeca-, eicosa- and tricosa-ynoic fatty acids containing acetylenic bonds were measured on non-polar stationary phase (dimethylsilicone with 5% phenyl groups). An unusually large increase in retention is observed for compounds containing conjugated and methylene interrupted acetylenic bonds. The additional increase in retention index as a result of the presence of one conjugated acetylenic bond is roughly equivalent to the retention increase caused by lengthening of the hydrocarbon chain for one carbon atom. The increase in retention for methylene interrupted bonds constitutes approximately 50% increase for conjugated triple bonds. A further increase in interruption substantially decreases the effect. Based on available literature data and the results of this work, the contributions of conjugated acetylenic and olefinic bonds, and methylene interrupted acetylenic bonds to retention were estimated.
在非极性固定相（含5%苯基的二甲基硅氧烷）上测定了含有炔键的十八碳、二十碳和二十三碳炔酸的甲酯和三甲基硅酯的保留指数。对于含有共轭和亚甲基间断炔键的化合物，观察到保留值异常大幅增加。由于存在一个共轭炔键导致的保留指数额外增加大致相当于烃链延长一个碳原子所引起的保留增加。亚甲基间断键导致的保留增加约为共轭三键的50%。间断程度的进一步增加会大幅降低这种影响。基于现有文献数据和本工作的结果，估算了共轭炔键和烯键以及亚甲基间断炔键对保留的贡献。
