27807-95-0Relevant academic research and scientific papers
Mechanism of Geometrical Isomerization about the Carbon- Nitrogen Double Bond
Asano, Tsutomu,Okada, Toshio,Herkstroeter, William G.
, p. 379 - 383 (1989)
For pyrazolone azomethines and N-benzylideneanilines, we report kinetic effects of pressure, solvent, and substituent on geometrical isomerization about the carbon-nitrogen double bond.Our results demonstrate the versatility of the inversion mechanism in these two groups of compounds.Invalidated is the rotation mechanism that had been previously predicted for pyrazolone azomethines with electron-donating substituents in the para position of the aromatic ring attached to the imino nitrogen.Contrary to azobenzene, mere push-pull substitution in N- benzylideneanilines is not enough to realize the rotation mechanism even in a relatively polar solvent such as methanol.
Nitrone/Imine Selectivity Switch in Base-Catalysed Reaction of Aryl Acetic Acid Esters with Nitrosoarenes: Joint Experimental and Computational Study
Volpe, Chiara,Meninno, Sara,Roselli, Angelo,Mancinelli, Michele,Mazzanti, Andrea,Lattanzi, Alessandra
supporting information, p. 5457 - 5466 (2020/10/12)
Herein we report a mild and diastereoselective access to ketonitrones by reacting easily available aryl acetic acid esters and other active methylene compounds, with nitrosoarenes under catalytic loading of 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) at room temperature. Depending on the substitution pattern and nature of the aryl moiety, a switch toward the formation of imines can be observed. The mechanistic framework is put to scrutiny by experimental and theoretical studies, pointing to the formation of a nitroso aldol intermediate, whose fate toward one of the competing pathways, namely hydride transfer or elimination, would depend upon the NOH/CHα relative acidities. (Figure presented.).
