Acetyl chloride, acetic anhydride alcoholysis

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

The same synthetic approach was used for the preparation of cyclic anhydrides [39- 3]. It was known before that succinic and glutaric acid form cyclic anhydrides which do not polymerize (see Formula 3.1, bottom). HiU and Carothers studied the reactions of higher dicarboxylic acids with acetyl chloride or acetic anhydride. In aU cases, polymeric anhydrides were obtained which were supposed to possess mixed anhydride end groups containing acetyl residues. The sensitivity to hydrolysis alcoholysis and phenolysis prevented exact molar mass measurements. However, a reliable distinction from monomeric cyclic anhydrides was achieved by reaction with aniline, because cyclic anhydrides can only yield one reaction product. When the polymeric anhydrides were heated to 150 °C in vacuum they degraded almost completely by back-biting . In this way 10 new cyclic anhydrides were isolated. These cyclic anhydrides underwent rapid polymerization in contact with traces of moisture. 

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