In this study,a new analytical technique was developed for the identification and quantification of multifunctional compounds containing simultaneously at least one hydroxyl or one carboxylic group,or both.This technique is based on derivatizing first the carboxylic group(s) of the multifunctional compound using an alcohol (e.g.,methanol,1-butanol) in the presence of a relatively strong Lewisacid (BF3) as a catalyst.This esterification reaction quickly and quantitatively converts carboxylic acids to their ester forms.The second step is based on silylation of the ester compounds using bis(trimethylsilyl) trifluoroacetamide (BSTFA) as the derivatizing agent.For compounds bearing ketone groups in addition to carboxylic and hydroxyl groups,a third step was used based on PFBHA derivatizationof the carbonyls.Different parameters including temperature,reaction time,and effect due to artifacts were optimized.A GC/MS in EI and in methane-CI mode was used for the analysis of these compounds.The new approach was tested on a number of multifunctional compounds.The interpretation of their EI (70 eV) and CI mass spectra shows that critical information is gained leading to unambiguous identification of unknown compounds.For example,when derivatized only with BF3-methanol,their mass spectra comprise primary ions at m/z M ·+ +1,M ·+ +29,and M ·+ - 31 for compounds bearing only carboxylic groups and M ·+ +1,M ·+ +29,M ·+ -31,and M ·+ -17 for those bearing hydroxyl andcarboxylic groups.However,when a second derivatization (BSTFA) was used,compounds bearing hydroxyl and carboxylic groups simultaneously show,in addition to the ions observed before,ions at m/z M ·+ +73,M ·+ -15,M ·+ -59,M ·+ -75,M ·+ -89,and 73.To the best of our knowledge,this technique describes systematically for the first time a method for identifying multifunctional oxygenated compounds containing simultaneously one or more hydroxyl and carboxylic acid groups.
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