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

使用碗型取代基稳定杂原子不稳定化学物质

基本信息

批准号：
12640575
负责人：
TAKENAKA Keiko
金额：
$ 2.18万
依托单位：
Japan Women's University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

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.

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将导致新的结构和反应性，因此我们对-S-N=O和-O-N=S的合成产生了兴趣，它们是-X-Y=Z类型的不稳定化合物。尽管有一些稳定的脂肪族.S-亚硝基硫醇(-S-N=O)，但尚未报道稳定的芳香族S-亚硝基硫醇。此外，尚未合成稳定的O-硫代亚硝基醇(-ON=S)。我们尝试利用碗型取代基Bmt作为空间保护基团来合成这些化合物。通过相应硫醇的亚硝化合成了第一个稳定的芳香族S-亚硝基硫I，BmtSNO，并通过X射线晶体学确定了结构。进行了氧化反应以及与一些亲核试剂的反应。尝试用 Bmt 基团或另一个空间保护基团 2,6-Dipp2QH3 基团合成第一个 O-硫代亚硝基醇。将芳香族卤化物转化为苯酚衍生物，然后用一些胺化试剂通过选择保护基团将其胺化，得到羟胺。有趣的是，BmtOH 的胺化引起重排，得到邻氨基苯酚衍生物。重排产物的分子结构为。通过X射线晶体学建立。尽管第一个O-硫代亚硝基醇是通过与二氯化硫反应合成的，但其分离并未成功。