145771-83-1Relevant academic research and scientific papers
Formation of a Tunneling Product in the Photorearrangement of o-Nitrobenzaldehyde
Gerbig, Dennis,Schreiner, Peter R.
, p. 9445 - 9448 (2017)
The photochemical rearrangement of o-nitrobenzaldehyde to o-nitrosobenzoic acid, first reported in 1901, has been shown to proceed via a distinct ketene intermediate. In the course of matrix isolation experiments in various host materials at temperatures as low as 3 K, the ketene was re-investigated in its electronic and vibrational ground states. It was shown that hitherto unreported H-tunneling dominates its reactivity, with half-lives of a few minutes. Unexpectedly, the tunneling product is different from o-nitrosobenzoic acid formed in the photoprocess: Once prepared by irradiation, the ketene spontaneously rearranges to an isoxazolone via an intriguing mechanism initiated by H-tunneling. CCSD(T)/cc-pVTZ computations reveal that this isoxazolone is neither thermodynamically nor kinetically favored under the experimental conditions, and that formation of this unique tunneling product constitutes a remarkable and new example of tunneling control.
Ultrafast irreversible phototautomerization of o-nitrobenzaldehyde
Migani, Annapaola,Leyva, Veronica,Feixas, Ferran,Schmierer, Thomas,Gilch, Peter,Corral, Ines,Gonzalez, Leticia,Blancafort, Lluis
, p. 6383 - 6385 (2011)
o-Nitrobenzaldehyde is photolabile because of an irreversible phototautomerization, whereas comparable aromatic compounds function as photoprotectors because the tautomerization is reversible. In this experimental and theoretical study we track down the c
Impact of vibrational excitation on the kinetics of a nascent ketene
Schmierer, Thomas,Schreier, Wolfgang J.,Koller, Florian O.,Schrader, Tobias E.,Gilch, Peter
, p. 11596 - 11607 (2009)
The formation and decay of a ketene intermediate photochemically formed from o-nitrobenzaldehyde has been studied by femtosecond UV/Vis and IR spectroscopy. The ketene is formed predominantly within a few 100 fs and to a minor extent within ～200 ps via th
Evidence for a ketene intermediate in the photochemical transformation of matrix-isolated o-nitrobenzaldehyde
Kuberski, Slawomir,Gebicki, Jerzy
, p. 105 - 110 (2007/10/02)
The ketene intermediate generated upon photolysis at 313 or 350 nm of matrix-isolated o-nitrobenzaldehyde was stabilized and characterized by UV-vis and IR spectroscopy.Further irradiation resulted in the formation of o-nitrosobenzoic acid along with N-hydroxybenzisoxazolone.Exclusive formation of the acid was observed when photolysis was carried out at wavelength greater than 357 nm.
