Oxidation reactions of acetylenic fatty esters with selenium dioxide/tert-butyl hydroperoxide.
Reaction of methyl undec-10-ynoate (1) with selenium dioxide/tert-butyl hydroperoxide (TBHP) in aqueous dioxane gave methyl 9-oxo-undec-10-ynoate (2, 9%) and 9-hydroxy-undec-10-ynoate (3, 60%), while methyl octadec-9-ynoate (4) yielded mixtures of positional isomers of mono-keto (viz. methyl 8-oxo- and 11-oxo-octadec-9-ynoate, 5, 5%), hydroxy-keto (viz. methyl 8-hydroxy-11-oxo- and 11-hydroxy-8-oxo-octadec-9-ynoate, 6, 10%), and dihydroxy (viz. methyl 8,11-dihydroxy-octadec-9-ynoate, 7, 24%) derivatives. Similar treatment of a conjugated diacetylenic fatty ester (methyl octadeca-6,8-diynoate, 8) furnished a mixture of methyl 5-oxo- and 10-oxo-octadeca-6,8-diynoate (9, 12%) and a complex mixture of very polar products. Reaction of methyl octadec-11E-en-9-ynoate (methyl santalbate) (10) with selenium dioxide/TBHP in aqueous dioxane gave exclusively a mixture of regiospecific products, viz. methyl 8-oxo-octadec-11(E)Z-en-9-ynoate (11, 6%) and methyl 8-hydroxy-octadec-11E-en-9-ynoate (12, 70%). The structures of the various products were determined by a combination of spectroscopic and mass spectral analyses.
Jie
M S
MS
Department of Chemistry, University of Hong Kong. hrsclkj@hkucc.hku.hk
Pasha
M K
MK
Alam
M S
MS
D005227:Fatty Acids / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D010084:Oxidation-Reduction; D010545:Peroxides / Q000737:chemistry*; D018036:Selenium Compounds / Q000737:chemistry*; D064588:Selenium Oxides; D013055:Spectrophotometry, Infrared; D020122:tert-Butylhydroperoxide
D005227:Fatty Acids; D010545:Peroxides; D018036:Selenium Compounds; D064588:Selenium Oxides; D020122:tert-Butylhydroperoxide