期刊
ORGANIC & BIOMOLECULAR CHEMISTRY
卷 9, 期 7, 页码 2336-2344出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0ob00976h
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资金
- EPSRC [EP/C543122/1, EP/C543130/1]
- King's College London
- ARC Centre of Excellence for Free Radical Chemistry and Biotechnology [CEO 561607]
- Advantage West Midlands (AWM)
- European Regional Development Fund (ERDF)
- Engineering and Physical Sciences Research Council [EP/C543122/1, EP/C543130/1] Funding Source: researchfish
Acyclic bissulfonylnitroxides have never been isolated, and degrade through fragmentation. In an approach to stabilising a bissulfonylnitroxide radical, the cyclic, peri-substituted N,N-bissulfonylhydroxylamine, 2-hydroxynaphtho[1,8-de][1,3,2]dithiazine 1,1,3,3-tetraoxide (1), has been prepared by formal nitrogen insertion into the sulfur-sulfur bond of a sulfinylsulfone, naphtho[1,8-cd][1,2]dithiole 1,1,2-trioxide. The heterocyclic ring of 1 is shown to adopt a sofa conformation by X-ray crystallography, with a pseudo-axial hydroxyl group. N,N-Bissulfonylhydroxylamine 1 displays high thermal, photochemical and hydrolytic stability compared to acyclic systems. EPR analysis reveals formation of the corresponding bissulfonylnitroxide 2 upon oxidation of 1 with the Ce(IV) salts CAN and CTAN. Although 2 does not undergo fragmentation, it cannot be isolated, since hydrogen atom abstraction to reform 1 occurs in situ. The stability and reactivity of 1 and 2 are compared with the known cyclic benzo-fused N,N-bissulfonylhydroxylamine, N-hydroxy-O-benzenedisulfonimide (6), for which the X-ray data, and EPR of the corresponding nitroxide 10, are also reported for the first time.
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