Analysis of hydroxypipecolic acids by gas chromatography-mass spectrometry

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

“…Other compounds examined are α-tocopherol (vitamin E) (Liebler et al, 1996), hydroxypipecolic acids (Kitew & Hughes, 1979), menthols (Bournot et al, 1971), tetracyclines (Tsuji & Robertson, 1973), hydroxynoraporphines (Evans & Vouros, 1978), nicotinamine (Ripperger, 1993), flavonoids (Füzfai & Molnár-Perl, 2007), bisphenol A (Szyrwińska et al, 2007), phytoestrogens (Ferrer et al, 2009), haplamine (Ea et al, 2014), cucurbic acid (Rontani et al, 2016), mycolic acids (Kaneda et al, 1966), N,Ndialkyl aminoethane-2-ols (Reddy et al, 2006), tricothecenes (Rodrigues-Fo et al, 2002), β-diketone-containing plant waxes (Tulloch & Hogge, 1978), alkoxychlorohydrins (Zenkevich & Drugov, 1987), abietic acids (Azemard et al, 2016;Rontani et al, 2015), pectic oligosaccharides from artichoke (Sabater et al, 2019), lignans (Boldizsár, et al, 2010), vitamin B6 (Richter, et al, 1967) and polysaccharides from the Chinese medicinal herb Anemarrhena asphodeloides Bunge (Xia et al, 2018). Spectra of these compounds are mainly formed by α-cleavages or cleavages and/or rearrangements of rings and do not present significant SCHEME 168.…”

Monomethyl ethers of 4,5-dihydroxypipecolic acid from Petaladenium urceoliferum : Enigmatic chemistry of an enigmatic legume

“…epimer 2. This assignment agrees with the TMS derivative of 1 having the shortest retention time of 1-3 as it has both C-4 and C-5 substituents in the axial orientation; it is known that of the four epimers of 4,5-dihydroxypipecolic acid the derivatized epimer with both substituents orientated axially elutes first (Kite and Hughes, 1997).…”

“…2); only trace amounts of dihydroxypipecolic acids were detected in the preparation made from the recently collected material (BI-22872). The dihydroxypipecolic acids were identified as (2S,4R,5R)-4,5-dihydroxypipecolic acid ( = L-trans-4-trans-5-dihydroxypipecolic acid, 4), (2S,4S,5R)-4,5-dihydroxypipecolic acid ( = L-cis-4-cis-5-dihydroxypipecolic acid, 5) and (2S,4R,5S)-4,5-dihydroxypipecolic acid ( = L-trans-4-cis-5-dihydroxypipecolic acid, 6) by the methods of Kite and Hughes (1997). Also present in the analysis of sample BI-24688 was (2S,4S)-4-hydroxypipecolic acid ( = L-trans-4-hydroxypipecolic acid, 7).…”

Differentiation of epimeric mono- and dihydroxypipecolic acids by negative ion sequential mass spectrometry

“…4 Recently, though, it was demonstrated that the trimethylsilyl derivatives of all eight mono-and dihydroxypipecolic acids could be separated by gas chromatography (GC). 5 However, the electron ionization mass spectra obtained in GC/MS analysis are very similar among the derivatised mono-and dihydroxylated isomers and so retention indices have to be calculated to obtain unambiguous identifications. Nevertheless, GC/MS analysis has permitted large surveys of hydroxypipecolic acid chemistry which would otherwise not have been feasible.…”

“…The advantage of the chromatographic resolution obtained with GC/MS outweigh some of the problems encountered, such as multiple derivative formation. 5 However, LC/MS is a valuable complementary technique, particularly when analysing extracts containing only one accumulated hydroxypipecolic acid. With GC/MS, analysis of such extracts is more difficult to interpret than analyses of extracts containing many hydroxypipecolic acids because certain pairs of compounds have very similar retention times.…”