71759-33-6Relevant articles and documents
Diarylamines with the Neighboring Pyridyl Group: Synthesis and Modulation of the Amine Functionality via Intramolecular H-Bonding
Grishin, Yuri K.,Klimchuk, Ivan A.,Levitskiy, Oleg A.,Magdesieva, Tatiana V.,Roznyatovsky, Vitaly A.,Tarasevich, Boris N.
supporting information, (2021/12/09)
New pyridyl-containing diarylamines were obtained via Cuassisted reductive amination of the ortho-2-pyridylarylboronic acids. Comparative analysis of the spectral and electrochemical data obtained for new diarylamines and their pyridyl-free counterparts revealed the intramolecular H-bond (IMHB) formation which significantly influences the properties of the amino group. The electron density at the N atom of the amino group is increased due to partial weakening of the N-H bond, although the BDE and activation energy for the H-atom abstraction is increased due to the chelating effect of two N atoms. The orthopyridyl-containing diarylamines are more prone to be oxidized as compared to their pyridyl-free counterparts; the shift in the oxidation potential values correlates with the strength of the intramolecular Hbonding which can be tuned by inserting substituents in the pyridyl or phenyl rings. The IMHB is reserved even in polar solvents having a significant H-acceptor ability (such as DMSO) but can be destroyed in methanol, testifying in favor of the dynamic nature of the H-bonding.
N-acylaminophenylcyclopropanes in reaction with nitrous acid generated in situ
Mochalov,Gazzaeva,Kadzhaeva,Fedotov,Trofimova
, p. 1415 - 1429 (2014/07/21)
The reaction of N-acylaminophenylcyclopropanes with HNO2 proceeds regioselectively with introduction of an N=O fragment into the three-membered ring and formation of the corresponding Δ2-isoxazolines. For ortho-substituted N-acylaminophenylcyclopropanes side processes were observed, caused by the intramolecular participation of the N-acyl group in conversions of the carbenium ions formed on opening the cyclopropane ring under the action of the nitrosating reagent, and by direct insertion of the modified ortho substituent into the three-membered ring.