2002 Fiscal Year Final Research Report Summary
Stabilization of Unstable Chemical Species with Heteroatoms using a Bowl-type Substituent
| Project/Area Number |
12640575
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | Japan Women's University |
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Principal Investigator |
TAKENAKA Keiko Japan Women's University, Faculy of Science, Reseach Associate, 理学部, 助手 (00130740)
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| Co-Investigator(Kenkyū-buntansha) |
OKAZAKI Renji Japan Women's University, FacuIty of Science, Professor, 理学部, 教授 (70011567)
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| Project Period (FY) |
2000 – 2002
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| Keywords | unstable chemical species / 5-nitrosothiois / O-thionitroso alcohol / steric protection group / reaction bowl |
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| Research Abstract |
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.
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Research Products
(2 results)
