Please use this identifier to cite or link to this item: https://hdl.handle.net/1959.11/11413
Title: A computational investigation of the structure of the novel anomeric amide N-azido-N-methoxyformamide and its concerted decomposition to methyl formate and nitrogen
Contributor(s): Glover, Stephen  (author)orcid ; Rauk, Arvi (author)
Publication Date: 2002
DOI: 10.1039/B204232K
Handle Link: https://hdl.handle.net/1959.11/11413
Abstract: Treatment of N-alkoxy-N-chloro- or N-acetoxyamides with sodium azide in aqueous acetonitrile results in Sɴ2 displacement of chlorine or acetate and the formation of reactive N-alkoxy-N-azidoamides which undergo a concerted decomposition to esters and nitrogen. The properties of the model N-azido-N-methoxyformamide have been computed at the B3LYP/6-31G* hybrid density functional level of theory. It is a typical anomeric amide in that the nitrogen is strongly sp³ hybridised resulting in a low amide isomerisation barrier. It decomposes in a two-step process involving exothermic loss of N₂ to give 1-formyl-1-methoxydiazene which spontaneously undergoes a HERON decomposition to methyl formate and N₂. Overall, the process is highly exothermic (ΔG between −654 and −659 kJ mol−¹). The competitive one-step HERON process involving formation of methyl formate and tetrazene is kinetically unfavourable. Sterically hindered ester formation will be facilitated by both exothermicity and a transition state for ester formation which avoids a sterically crowded tetrahedral intermediate.
Publication Type: Journal Article
Source of Publication: Journal of the Royal Chemical Society: Perkin Transactions 2 (10), p. 1740-1746
Publisher: Royal Society of Chemistry
Place of Publication: United Kingdom
ISSN: 1364-5471
1472-779X
Fields of Research (FoR) 2008: 030505 Physical Organic Chemistry
Socio-Economic Objective (SEO) 2008: 970103 Expanding Knowledge in the Chemical Sciences
Peer Reviewed: Yes
HERDC Category Description: C1 Refereed Article in a Scholarly Journal
Appears in Collections:Journal Article

Files in This Item:
2 files
File Description SizeFormat 
Show full item record

SCOPUSTM   
Citations

24
checked on Aug 17, 2024

Page view(s)

1,288
checked on Apr 7, 2024
Google Media

Google ScholarTM

Check

Altmetric


Items in Research UNE are protected by copyright, with all rights reserved, unless otherwise indicated.