Transformation of fatty acid hydroperoxides by alkali and characterization of products |
| |
Authors: | Harold W Gardner Thomas D Simpson Mats Hamberg |
| |
Affiliation: | (1) Department of Physiological Chemistry, Karolinska Institutet, S-104 01 Stockholm, Sweden;(2) NCAUR, ARS, USDA, 1815 N. University Street, 61604 Peoria, IL |
| |
Abstract: | It has previously been determined that (13S,9Z,11E)-13-hydroperoxy-9,11-octadecadienoic acid was mainly converted into (13S,9Z,11E)-13-hydroxy-9,11-octadecadienoic acid by 5 N KHO with preservation of the stereochemistry of the reactant Simpson, T.D.,
and Gardner, H.W. (1993)Lipids 28, 325–330]. In addition, about 20–25% of the reactant was converted into several unknown by-products. In the present work
it was confirmed that the stereochemistry was conserved during the hydroperoxy-diene to hydroxydiene transformation, but also,
novel by-products were identified. It was found that after only 40 min reaction (9Z)-13-oxo-trans-11,12-epoxy-9-octadecenoic acid accumulated to as much as 7% of the total. Later, (9Z)-13-oxo-trans-11,12-epoxy-9-octadecenoic acid began to disappear, and several other compounds continued to increase in yield. Two of these
compounds, 2-butyl-3,5-tetradecadienedioic acid and 2-butyl-4-hydroxy-5-tetradecenedioic acid, were shown to originate from
(9Z)-13-oxo-trans-11,12-epoxy-9-octadecenoic acid, and they accumulated up to 2–3% each after 4 to 6 h. Some other lesser products included
11-hydroxy-9,12-heptadecadienoic acid, 3-hydroxy-4-tridecenedioic acid, 13-oxo-9,11-octadecadienoic acid and 12,13-epoxy-11-hydroxy-9-octadecenoic
acid. Except for the latter two, most or all of the compounds could have originated from Favorskii rearrangement of the early
product, (9Z)-13-oxo-trans-11,12-epoxy-9-octadecenoic acid, through a cyclopropanone intermediate. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|