Please use this identifier to cite or link to this item:
https://hdl.handle.net/1959.11/11413
Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Glover, Stephen | en |
dc.contributor.author | Rauk, Arvi | en |
dc.date.accessioned | 2012-10-12T13:45:00Z | - |
dc.date.issued | 2002 | - |
dc.identifier.citation | Journal of the Royal Chemical Society: Perkin Transactions 2 (10), p. 1740-1746 | en |
dc.identifier.issn | 1364-5471 | en |
dc.identifier.issn | 1472-779X | en |
dc.identifier.uri | https://hdl.handle.net/1959.11/11413 | - |
dc.description.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. | en |
dc.language | en | en |
dc.publisher | Royal Society of Chemistry | en |
dc.relation.ispartof | Journal of the Royal Chemical Society: Perkin Transactions 2 | en |
dc.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 | en |
dc.type | Journal Article | en |
dc.identifier.doi | 10.1039/B204232K | en |
dc.subject.keywords | Physical Organic Chemistry | en |
local.contributor.firstname | Stephen | en |
local.contributor.firstname | Arvi | en |
local.subject.for2008 | 030505 Physical Organic Chemistry | en |
local.subject.seo2008 | 970103 Expanding Knowledge in the Chemical Sciences | en |
local.profile.school | School of Science and Technology | en |
local.profile.email | sglover@une.edu.au | en |
local.output.category | C1 | en |
local.record.place | au | en |
local.record.institution | University of New England | en |
local.identifier.epublicationsrecord | pes:92 | en |
local.publisher.place | United Kingdom | en |
local.format.startpage | 1740 | en |
local.format.endpage | 1746 | en |
local.identifier.scopusid | 0036026294 | en |
local.peerreviewed | Yes | en |
local.identifier.issue | 10 | en |
local.contributor.lastname | Glover | en |
local.contributor.lastname | Rauk | en |
dc.identifier.staff | une-id:sglover | en |
local.profile.orcid | 0000-0002-9344-8669 | en |
local.profile.role | author | en |
local.profile.role | author | en |
local.identifier.unepublicationid | une:11612 | en |
dc.identifier.academiclevel | Academic | en |
local.title.maintitle | A computational investigation of the structure of the novel anomeric amide N-azido-N-methoxyformamide and its concerted decomposition to methyl formate and nitrogen | en |
local.output.categorydescription | C1 Refereed Article in a Scholarly Journal | en |
local.search.author | Glover, Stephen | en |
local.search.author | Rauk, Arvi | en |
local.uneassociation | Unknown | en |
local.identifier.wosid | 000178314300016 | en |
local.year.published | 2002 | en |
Appears in Collections: | Journal Article |
Files in This Item:
File | Description | Size | Format |
---|
SCOPUSTM
Citations
24
checked on Jul 20, 2024
Page view(s)
1,288
checked on Apr 7, 2024
Items in Research UNE are protected by copyright, with all rights reserved, unless otherwise indicated.