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

具有不稳定官能团的化合物通常具有较高的反应活性。由于不稳定化学物质的发展会导致新的结构和反应性，我们对-S-N=O和-O-N=S的合成产生了兴趣，这是-X-Y=Z型的不稳定化合物。虽然有些稳定的脂肪族。s -亚硝基硫醚（-S-N=O），没有稳定的芳香型s -亚硝基硫醚的报道。此外，还没有合成稳定的o -硫代硝基醇（-ON=S）。我们尝试利用碗型取代基Bmt作为位位保护基团来合成这些化合物。通过相应的硫醇亚硝化合成了第一个稳定的芳香s -亚硝基硫代化合物BmtSNO，并通过x射线晶体学确定了其结构。对其进行了氧化和与一些亲核试剂的反应。尝试用Bmt基团或另一个位保护基团2,6- dipp2qh3合成第一个o -亚硝基醇。芳香族卤化物被转化为苯酚衍生物，然后与一些活性试剂胺化，通过选择一个保护基团得到羟胺。有趣的是，BmtOH的胺化引起重排，得到邻氨基酚衍生物。重组产物的分子结构为。由x射线晶体学建立。虽然用二氯化硫合成了第一个o -亚硝基醇，但其分离不成功。

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.