GAS CHROMATOGRAPHIC-MASS SPECTROMETRIC STUDY OF REACTIONS OF HALODEOXYCELLULOSES WITH THIOLS IN AQUEOUS-SOLUTIONS

Chloro- and bromodeoxycelluloses with high degrees of substitution, prepared with halosuccinimide and triphenylphosphine under homogeneous conditions, were treated with eight thiols under moderately alkaline conditions. Bromodeoxycellulose was generally more reactive than chlorodeoxycellulose and carboxyl-bearing thiols such as mercaptoacetic acid were less reactive than neutral thiols such as benzenethiol. The maximum conversion of halodeoxyglucose units to thio derivatives was 65%. When the reaction was run at high alkalinity at 60 degrees C, elimination of hydrogen halide to yield 3,6-anhydroglucose and/or 5,6-glucosene units took place appreciably as a side reaction. Hydrolysates of the reaction products with thiols having no carboxyl group were analyzed by gas chromatography-mass spectrometry as trifluoroacetates and the formation of S-substituted 6-thio-6-deoxyglucose units was confirmed.