Synthesis of Isochalcogenazole Rings by Treating β-(<i>N</i>,<i>N</i>-Dimethylcarbamoylchalcogenenyl)alkenyl Ketones with Hydroxylamine-<i>O</i>-sulfonic Acid
作者:Kazuaki Shimada、Akiko Moro-oka、Akiko Maruyama、Hiroyuki Fujisawa、Toshio Saito、Ryo Kawamura、Hisashi Kogawa、Maiko Sakuraba、Yukichi Takata、Shigenobu Aoyagi、Yuji Takikawa、Chizuko Kabuto
DOI:10.1246/bcsj.80.567
日期:2007.3.15
β-(N,N-Dimethylcarbamoylselenenyl)- and β-(N,N-dimethylcarbamoyltellurenyl)alkenyl ketones were converted into isoselenazoles and isotellurazole Te-oxides, respectively, simply by treating with hydroxylamine-O-sulfonic acid, and deoxygenation of the latter products was successfully carried out by treating with PPh3. Alternative treatment of ynone oxime tosylates with hydrochalcogenide ions or N,N-dimethylchalcogenocarbamate ions also gave the same isochalcogenazole rings. These reactions were assumed to proceed through intramolecular nucleophilic substitution on the nitrogen atom of oxime sulfonates by the attack of in situ generated chalcogen nucleophiles.
β-(N,N-二甲基氨基甲酰硒基)- 和 β-(N,N-二甲基氨基甲酰月桂酰)烯基酮只需用羟胺-O-磺酸处理,就能分别转化为异硒唑和异碲唑羰基化合物。用氢化钙离子或 N,N-二甲基钙镁离子处理炔酮肟对甲苯磺酸盐,也能得到相同的异钙唑环。假定这些反应是通过肟磺酸盐的氮原子受到原位生成的醛基亲核物的攻击而发生的分子内亲核取代反应。