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Article
Synthesis, Structural Studies and Desilylation Reactions of Some N-2-(Trimethylsilyl)ethyl-N-nitrosocarbamates
Tetrahedron
  • Arpitha Thakkalapally, University of Dayton
  • Vladimir Benin, University of Dayton
Document Type
Article
Publication Date
5-1-2005
Abstract

The present report describes the preparation and characterization of several N-2-(trimethylsilyl)ethyl-N-nitrosocarbamates, designed as precursors to thermally unstable secondary N-nitrosocarbamate anions via fluoride-assisted cleavage. X-ray structural studies demonstrate that the core N-nitrosocarbamate moiety has a nearly planar geometry, with an s-E orientation at the N–N bond. DFT calculations (B3LYP/6-31+G(d)) reproduce accurately the structural features of the title compounds and detailed conformational analysis at the same level of theory addresses the long-standing issue of preferred geometries for three classes of related structures: N-nitrosocarbamates, N-nitrosoureas and N-nitrosoamides. Desilylation studies demonstrate that both the solvent and the fluoride concentration influence the rate of the process.

Inclusive pages
4939–4948
ISBN/ISSN
0040-4020
Document Version
Postprint
Comments

The document available for download is the authors' accepted manuscript, posted here in compliance with the publisher's policy on self-archiving.

Some differences may exist between this version and the publisher's version; as such, researchers wishing to quote directly from it are advised to consult the version of record, available at many libraries or from the publisher.

Permission documentation is on file.

Publisher
Elsevier
Peer Reviewed
Yes
Citation Information
Arpitha Thakkalapally and Vladimir Benin. "Synthesis, Structural Studies and Desilylation Reactions of Some N-2-(Trimethylsilyl)ethyl-N-nitrosocarbamates" Tetrahedron Vol. 61 Iss. 21 (2005)
Available at: http://0-works.bepress.com.library.simmons.edu/vladimir_benin/4/