In search of a new class of stable nitroxide: synthesis and reactivity of a peri-substituted N,N-bissulfonylhydroxylamine

Patel, Bhaven, Carlisle, Julie, Bottle, Steven E., Hanson, Graeme R., Kariuki, Benson M., Male, Louise, McMurtrie, John C., Spencer, Neil and Grainger, Richard S. (2011) In search of a new class of stable nitroxide: synthesis and reactivity of a peri-substituted N,N-bissulfonylhydroxylamine. Organic and Biomolecular Chemistry, 9 7: 2336-2344. doi:10.1039/c0ob00976h


Author Patel, Bhaven
Carlisle, Julie
Bottle, Steven E.
Hanson, Graeme R.
Kariuki, Benson M.
Male, Louise
McMurtrie, John C.
Spencer, Neil
Grainger, Richard S.
Title In search of a new class of stable nitroxide: synthesis and reactivity of a peri-substituted N,N-bissulfonylhydroxylamine
Journal name Organic and Biomolecular Chemistry   Check publisher's open access policy
ISSN 1477-0520
1477-0539
Publication date 2011-01-01
Sub-type Article (original research)
DOI 10.1039/c0ob00976h
Open Access Status Not Open Access
Volume 9
Issue 7
Start page 2336
End page 2344
Total pages 9
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Formatted abstract
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.
Keyword Living Radical Polymerizations
Sulphur Nitrogen Compounds
O-Benzenedisulfonimide
Hydrogen Abstraction
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
Centre for Advanced Imaging Publications
 
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