Synthesis of hindered hydrazones and their reaction with thionyl chloride

Hydrazones 12a–c and ketazines 13a–c were prepared by the reaction of ketones 11a–c with hydrazine hydrate depending on the temperature and the reaction time. Some ketone (aryl)hydrazone derivatives 14a,c,e reacted with thionyl chloride to afford the chlorothiadiazoline derivatives 15a–c. Surprisingly, the chlorine atom in the latter compounds was found to undergo smooth nucleophilic substitution, and by boiling these compounds in absolute ethanol gave the corresponding ethoxythiadiazoline derivatives 16a–c. The structure of the ethoxythiadiazoline 16b was confirmed by single crystal X‐ray determination. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:223–228, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10125