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Gas chromatography‐mass spectrometry of methyl esters of unsaturated oxygenated fatty acids
Author(s) -
Kleiman R.,
Spencer G. F.
Publication year - 1973
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/bf02886864
Subject(s) - chemistry , allylic rearrangement , silylation , methylene , degree of unsaturation , double bond , methyl group , epoxide , fragmentation (computing) , bond cleavage , cleavage (geology) , mass spectrometry , mass spectrum , medicinal chemistry , conjugated system , stereochemistry , organic chemistry , alkyl , ion , catalysis , chromatography , polymer , geotechnical engineering , fracture (geology) , computer science , engineering , operating system
Silylation of hydroxyl groups in methyl esters of unsaturated hydroxy acids provides compounds that give mass spectra which can be readily interpreted, whereas spectra of underivatized esters are extremely difficult to evaluate. The relationship of the double bond(s) to the trimethylsiloxy (TMS) group results in specific mass spectral patterns. In esters that have the TMS group separated from the double bond by one methylene group, the ions caused by α ‐cleavage at the TMS group on the side closest to the olefinic group are much more abundant than those produced from α ‐cleavage on the other side of the TMS group. In esters that have the TMS group and the double bond separated by two methylene groups, α ‐cleavage ions are approximately equal. When the TMS group and the double bond are allylic, no fragmentation results between them. Cleavage does occur on either side of this system, and those ions resulting from cleavage alpha to the TMS group are in greatest abundance. Silylation of esters that have a conjugated diene or ene‐yne system adjacent to a hydroxyl group also gives derivatives amenable to gas chromatographymass spectrometry. In these esters, large peaks are observed that arise from α ‐cleavage at the TMS group and at the other end of the olefinic system. No fragmentation between the TMS group and the sites of unsaturation occurs. Unsaturated epoxy methyl esters produce spectra difficult to interpret. When the epoxide is converted to methoxy‐hydroxy derivatives by BF 3 ‐methanol, the spectrum locates the position of the epoxide group. Silylation of the hydroxyl group produces a compound that gives a less complicated spectrum which also locates the original epoxy group. Mass spectrometry of a series of unsaturated keto‐esters, without derivatization, provides spectra that are easily interpretable.