Factors Influencing the Autoxidation of Fatty Acids: Effect of Olefin Geometry of the Nonconjugated Diene
作者:Keri A. Tallman、Bill Roschek、Ned A. Porter
DOI:10.1021/ja049104q
日期:2004.8.1
Autoxidations of cis,cis, cis,trans, and trans,trans nonconjugated octadecadienoates and pentadecadienes were carried out in the presence of alpha-tocopherol to investigate the effect of olefin geometry on this oxidation process and provide insight into the factors that influence the autoxidation of fatty acids. We have found that as the trans character of the diene increases, the amount of O(2) trapping
在α-生育酚存在下进行顺式、顺式、顺式、反式和反式、反式非共轭十八碳二烯酸酯和十五碳二烯的自氧化,以研究烯烃几何结构对这种氧化过程的影响,并深入了解影响自氧化的因素脂肪酸。我们发现,随着二烯的反式特征的增加,在戊二烯基自由基的中心(双烯丙基)位置捕获的 O(2) 的量也会增加。此外,双烯丙基过氧自由基的β-碎片(k(beta) 大约10(6) s(-1)) 的速率常数在从顺式、顺式到反式、反式二烯的过程中下降。我们还发现,对于顺式,反式非共轭二烯,在 transoid 末端优先通过 O(2) 捕获戊二烯基,产生顺式,