CSIRO Publishing blank image blank image blank image blank imageBooksblank image blank image blank image blank imageJournalsblank image blank image blank image blank imageAbout Usblank image blank image blank image blank imageShopping Cartblank image blank image blank image You are here: Journals > Australian Journal of Chemistry   
Australian Journal of Chemistry
Journal Banner
  An international journal for chemical science
blank image Search
blank image blank image
blank image
  Advanced Search

Journal Home
About the Journal
Editorial Structure
For Advertisers
Online Early
Current Issue
Just Accepted
All Issues
Virtual Issues
Special Issues
Research Fronts
Sample Issue
For Authors
General Information
Submit Article
Author Instructions
Open Access
For Referees
Referee Guidelines
Review an Article
For Subscribers
Subscription Prices
Customer Service
Print Publication Dates

blue arrow e-Alerts
blank image
Subscribe to our Email Alert or RSS feeds for the latest journal papers.

red arrow Connect with us
blank image
facebook twitter LinkedIn

Affiliated with RACI

Royal Australian Chemical Institute
Royal Australian
Chemical Institute


Article << Previous     |     Next >>   Contents Vol 60(6)

Oxidation of Aromatic Alkynes with Nitrate Radicals (NO3): An Experimental and Computational Study on a Synthetically Highly Versatile Radical

Uta Wille A B C, Jilliarne Andropof A B

A School of Chemistry, University of Melbourne, Melbourne VIC 3010, Australia.
B Bio21 Molecular Science and Biotechnology Institute, 30 Flemington Road, Melbourne VIC 3010, Australia.
C Corresponding author. Email: uwille@unimelb.edu.au
PDF (435 KB) $25
 Supplementary Material
 Export Citation


Addition of electro- and photochemically generated nitrate radicals, NO3, to the C≡C triple bond of aromatic alkynes 9a9h leads to formation of 1,2-diketones 10a10h. Surprisingly, benzophenones 11a11h are obtained as by-products, which formally result from loss of a carbon atom. Density functional studies performed with the BHandHLYP method in combination with various basis sets revealed that 1,2-diketones result from 5-endo cyclization of the initially formed vinyl radical and loss of NO. The key step to benzophenone formation is a γ-cleavage at the stage of the vinyl radical with release of NO2, followed by Wolff rearrangement of the resulting α-oxo carbene.

Subscriber Login

Legal & Privacy | Contact Us | Help


© CSIRO 1996-2015