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
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
Collection year 2012
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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