TY - JOUR
T1 - Sparing the ortho-position in nucleophilic aromatic substitution-specific displacement of the 4-SePh group in 2,4-bis(phenylseleno)nitrobenzene
AU - Stuhr-Hansen, Nicolai
AU - Götze, Thorstein Finn
AU - Henriksen, Lars
AU - Sølling, Theis Ivan
AU - Langkilde, Annette
AU - Sørensen, Henning Osholm
PY - 2009
Y1 - 2009
N2 - 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
AB - 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
KW - Materials characterization and modelling
KW - Materials research
KW - Materialeforskning
KW - Materialekarakterisering og materialemodellering
U2 - 10.1002/hc.20519
DO - 10.1002/hc.20519
M3 - Journal article
SN - 1042-7163
VL - 20
SP - 101
EP - 108
JO - Heteroatom Chemistry
JF - Heteroatom Chemistry
IS - 2
ER -