Radical Dinitroalkane Dianions from the Nitration of Nitroalkanes by Peroxynitrite

Autor:	Bohle Ds, Hu Y, Arnold Ev
Rok vydání:	2000
Předmět:	Nitrates Free Radicals Geminal Spin trapping Electron Spin Resonance Spectroscopy General Medicine Toxicology Photochemistry Medicinal chemistry Nitroparaffins law.invention Adduct Homolysis chemistry.chemical_compound chemistry law Nitration Nitro Electron paramagnetic resonance Peroxynitrite
Zdroj:	Chemical Research in Toxicology. 13:963-966
ISSN:	1520-5010 0893-228X
DOI:	10.1021/tx0001474
Popis:	In alkaline solutions at pH >10, peroxynitrite (ONOO(-)) rapidly and efficiently nitrates aci-nitroalkane anions, RCH=NO(2)(-) (R = H, CH(3), or CH(3)CH(2)), to give the radical dinitrodianions, RC(NO(2))(2)(2-). These anions have been characterized by EPR and have multiplets based on 1:2:3:2:1 pentets consistent with a hyperfine coupling with two equivalent (14)N nuclei of the nitro groups, and the following hyperfine coupling constants, in gauss: R = H, a(N) = 9.96 and a(H) = 1.85; R = CH(3), a(N) = 9.90 and a(H) = 3.22; and R = CH(3)CH(2), a(N) = 9.57 and a(H) = 4.01. Nitration is attributed to the trapping of nitrogen dioxide, formed by ONO-OCO(2)(-) homolysis for the carbon dioxide adduct of peroxynitrite, by the aci-nitroalkane anion. In air, the radical dinitrodianions are oxidized to the monoanions, and the kinetics of its formation is readily followed by UV/vis spectroscopy of the rise in absorption at 380 nm. This report represents the first successful spin trapping of nitrogen dioxide formed from peroxynitrite, and the method may be a useful one for preparing geminal dinitroalkanes.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::1adb2fb5e8b61f531fbc563b131c6a58 https://doi.org/10.1021/tx0001474 Zobrazit plný text záznamu