Journal article
Sparing the ortho-position in nucleophilic aromatic substitution-specific displacement of the 4-SePh group in 2,4-bis(phenylseleno)nitrobenzene
University of Copenhagen1
Metal Structures in Four Dimensions, Materials Research Division, Risø National Laboratory for Sustainable Energy, Technical University of Denmark2
Materials Research Division, Risø National Laboratory for Sustainable Energy, Technical University of Denmark3
Risø National Laboratory for Sustainable Energy, Technical University of Denmark4
Upon treatment of o- and p(phenylseleno,)nitrobenzenes with sodium methoxide quantitative exchange reactions took place, affording the corresponding methoxynitrobenzenes. Upon reaction between 2,4-bis(phenylseleno)nitrobenzene 2 and sodium methoxide, an unusual regiopure formation of 4-methoxy-2-(phenylseleno)nitrobenzene 3 was observed.
This product remained unreactive toward an excess of sodium methoxide, thus preventing the for-mation of 2,4-dimethoxynitrobenzene 6. The nature of the reactants and of the intermediate Meisenheimer complexes was examined by synthetic investigations, x-ray crystallography, and DFT calculations. We found that the observed selectivity can be understood in terms of traditional resonance considerations. (C) 2009 Wiley Periodicals, Inc.
Heteroatom Chem 20:101-108, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20519
Language: | English |
---|---|
Publisher: | Wiley |
Year: | 2009 |
Pages: | 101-108 |
ISSN: | 10981071 and 10427163 |
Types: | Journal article |
DOI: | 10.1002/hc.20519 |
ORCIDs: | Sørensen, Henning Osholm , 0000-0003-1710-9072 and 0000-0003-2467-4205 |
Materialeforskning Materialekarakterisering og materialemodellering Materials characterization and modelling Materials research