Determination of the DS and substituent distribution of cationic alkyl polyglycosides and cationic starch ethers by GLC after dealkylation with morpholine

The total DS and substituent distribution of starch and alkyl polyglycosides functionalised as O-(2-hydroxy-3-trimethylammonium)propyl ethers were determined by GLC. To achieve volatile analytes, the samples were submitted to methanolysis, N-demethylation and O-trimethylsilylation. Alternatively hydrolysis, reduction with NaBH4 and subsequent O-acetylation were performed, but suffered from intramolecular acetal formation of 2-O-substituted residues, preventing reduction. Morpholine as nucleophile was superior to thiophenolate with regard to quantitative dealkylation and side product formation. The ratio of un-, mono-, di-, tri-, and tetrasubstituted compounds was determined. The total DS values calculated from these mole fractions were in good agreement with those obtained from elemental analysis or NMR from standards. Regioselectivity of the cationisation reaction was determined after methanolysis, permethylation and Hofmann elimination by GLC. (C) 2003 Elsevier Science Ltd. All rights reserved.