Stabilization of Unstable Chemical Species with Heteroatoms using a Bowl-type Substituent

点击翻译按钮获取中文摘要

Compounds with unstable functional groups generally have high reactivity. Since the development of unstable chemical species will lead to new structure and reactivity, we became interested in the synthesis of -S-N=O and -O-N=S, which are unstable compounds of -X-Y=Z type. Although some stable aliphatic .S-nitrosothioIs (-S-N=O), no stable aromatic S-nitrosothiol has been reported. Furthermore, no stable O-thionitrosoalcohol (-ON=S) has been synthesized. We attempted the synthesis of these compounds by taking advantage of a bowl-type subsitituent, Bmt, as a steric protection group.The first stable aromatic S-nitrosothioI, BmtSNO, was synthesized by the nitrosation of the corresponding thiol and the structure was established by X-ray crystallography. Its oxidation and reactions with some nuclephiles were carried out. Synthesis of the first O-thionitrosoalcohol was attempted with Bmt group or another steric protection group, 2,6-Dipp2QH3 group. Aromatic halides were converted to phenol derivatives, which were then aminated with some animating reagents to give hydroxylamine by selecting a protection group. Interestingly, the amination of BmtOH caused rearrangement to give an o-aminophenol derivative. The molecular structure of the rearranged product was. established by X-ray crystallography. Although the first O-thionitrosoalcohol was synthesized by the reaction with sulfur dichloride, its isolation was unsuccessful.