Determination of the Composition of Acetylglycerol Mixtures by 1H NMR Followed by GC Investigation

Abstract

Commercially available partly acetylated glycerols (mono- and diacetins) are a mixture of glycerol, 1- and 2-acetylglycerol, 1,2- and 1,3-diacetylglycerol, and triacetin. No exact analysis method is available. Comparisons of (1)H NMR measurements obtained using deuterated dimethyl sulfoxide (DMSO-d6) and DMSO-d6/15% D2O are sufficient to identify and determine quickly all the components. Advantages compared with the commonly used NMR solvent CDCl3 for fatty acid glycerides include the solubility of all the components and a highly informative OH signal pattern in a region between 4.36 and 5.26 ppm almost free of other signals. 2-Acetylglycerol (2-acetin) is shown to disproportionate even at 50 degrees C into a mixture of glycerol and acetylglycerol thereby making it difficult to quantify by liquid chromatography (LC) and gas chromatography (GC) methods. Complete (1)H chemical shift data for all five components allow for the identification of the components in the mixture and thus the determination of the composition. The NMR method with DMSO-d6 as solvent was used for acetins, propionins, and butyrins. Semipreparative high-performance liquid chromatography (HPLC) on an RP18 column led to moderately pure 1-monoacetin and a mixture of diacylated species. Electron impact mass spectra show for all the components very characteristic fragmentation patterns with loss of AcOCH2 radicals, in contrast to the well-known pattern of longer-chained fatty acid derivatives that show preferred first-step loss of acyl-O radicals.