Disclosed is a method of chlorinating a carbohydrate or derivative thereof, for example, a sucrose-6-ester at the 4,1′, and 6′ positions, with irreversible removal of HCl formed during the reaction to form the chlorinated carbohydrate or derivative thereof, for example, a 4,1′,6′-trichloro-4,1′,6′-trideoxy-6-O-ester of galactosucrose (TGS-6E). The irreversible removal of HCl can be carried out by an irreversible physical process and/or an irreversible chemical process. Sucralose, an artificial sweetener, can be prepared by deesterification of the TGS-6E. The chlorination reaction takes place at low temperatures and the desired chlorinated product is obtained in high yields and in high purities.