%0 Journal Article %1 ISI:000081603000020 %A Eckert, Frank %A Rauhut, Guntram %A Katritzky, Alan R. %A Steel, Peter J. %D 1999 %J J. Am. Chem. Soc. %K chemie imported from:alexanderdenzel rauhut theoretische stuttgart theochem %N 28 %P 6700–6711 %R 10.1021/ja990475u %T A theoretical and experimental study of the molecular rearrangement of 5-methyl-4-nitrobenzofuroxan %U http://dx.doi.org/10.1021/ja990475u %V 121 %X The molecular rearrangement of 5-methyl-4-nitrobenzofuroxan to 7-methyl-4-nitrobenzofuroxan was studied by means of ab initio and density functional theory. Experimentally obtained IR spectra and X-ray data support the applicability of the theoretical methods and allow for a complete assignment of the vibrational modes. The influence of the methyl substituent on the underlying tautomeric reaction was investigated in detail. Trends for the reactivity of 4-nitrobenzofuroxans with substituents in the 5-position were established on the basis of an energy partitioning, providing insight into the driving forces of the Boulton-Katritzky rearrangement. Rate constants were calculated for this reaction using different implementations of variational transition-state theory. Ln addition a reaction yielding 6-methyl-7-nitrobenzofuroxan was investigated as an alternative to the rearrangement: considered. An accurate treatment of relative energies of this competing reaction requires very demanding computational methods which could not be applied here. Therefore, energy corrections were estimated from smaller benchmark systems. %@ 0002-7863

@article{ISI:000081603000020, abstract = {The molecular rearrangement of 5-methyl-4-nitrobenzofuroxan to 7-methyl-4-nitrobenzofuroxan was studied by means of ab initio and density functional theory. Experimentally obtained IR spectra and X-ray data support the applicability of the theoretical methods and allow for a complete assignment of the vibrational modes. The influence of the methyl substituent on the underlying tautomeric reaction was investigated in detail. Trends for the reactivity of 4-nitrobenzofuroxans with substituents in the 5-position were established on the basis of an energy partitioning, providing insight into the driving forces of the Boulton-Katritzky rearrangement. Rate constants were calculated for this reaction using different implementations of variational transition-state theory. Ln addition a reaction yielding 6-methyl-7-nitrobenzofuroxan was investigated as an alternative to the rearrangement: considered. An accurate treatment of relative energies of this competing reaction requires very demanding computational methods which could not be applied here. Therefore, energy corrections were estimated from smaller benchmark systems.}, added-at = {2019-02-15T17:47:58.000+0100}, author = {Eckert, Frank and Rauhut, Guntram and Katritzky, Alan R. and Steel, Peter J.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2718f467b385a9542ef1668d48471f521/theochem}, doi = {10.1021/ja990475u}, interhash = {2ce48341562e8b1eeb879ede7d382165}, intrahash = {718f467b385a9542ef1668d48471f521}, isbn = {0002-7863}, issn = {00027863}, journal = {J. Am. Chem. Soc.}, keywords = {chemie imported from:alexanderdenzel rauhut theoretische stuttgart theochem}, month = jul, number = 28, pages = {6700–6711}, timestamp = {2019-02-15T16:47:58.000+0100}, title = {{A theoretical and experimental study of the molecular rearrangement of 5-methyl-4-nitrobenzofuroxan}}, url = {http://dx.doi.org/10.1021/ja990475u}, volume = 121, year = 1999 }