34631-58-8Relevant academic research and scientific papers
The chemistry of peroxynitrite: Involvement of an ET process in the radical nitration of unsaturated and aromatic systems
Grossi, Loris,Montevecchi, Pier Carlo,Strazzari, Samantha
, p. 741 - 748 (2001)
Reactions of peroxynitrous acid, HPN, with styrene under acidic conditions lead to the oxime 1, the nitrate 2, benzaldehyde (3), and α-nitroacetophenone (4) in overall yields that depend strongly on the pH value and with a product distribution that depends on the dioxygen concentration. The results are rationalized by assuming that HPN undergoes acid-catalyzed decomposition to give nitrous anhydride, or its synthetic equivalent, which is responsible for the regioselective nitration of the styrene double bond by an ET process. The resulting β-nitrobenzyl radical 6 can, depending on the reaction conditions, undergo reversible coupling with nitric oxide to afford the nitroso derivative 7 and then the tautomeric oxime 1, or trapping by dioxygen, eventually leading to products 2, 3, and 4 through the intermediacy of the peroxynitrite derivative 8. Oxime 1 and nitrate 2 are also obtained by treating styrene with nitrous anhydride under protic conditions, the latter being produced in situ from nitric oxide/dioxygen. Similarly to styrene, 1,4-diphenylbutadiene (14) gives radicals 22 and 21 by competitive trapping at the side chain and at the aromatic ring. In turn, radicals 22 and 21 undergo β-fragmentation reactions or trapping by dioxygen with eventual formation of nitrates 16 and 17, cinnamic aldehyde (18), and the diol 15. Finally, the HPN-promoted reaction of p-cresol (27) leads to the 2-nitro derivative 28 through an initial electron-transfer process followed by in cage recombination of the resulting radical ion pair.
Formation and Thermal Cleavage Reactions of the Cycloadduct of 9,10-Dimethylanthracene and Nitrosyl Cyanide
Horsewood, Peter,Kirby, Gordon W.,Sharma, Ram Prakash,Sweeny, James
, p. 1802 - 1806 (2007/10/02)
Nitrosyl cyanide and 9,10-dimethylanthracene (DMA) (2) reacted at -25 deg C to form the crystallyne cycloadduct, 9,10-dihydro-9,10-(N-cyanoepoxyimino)-9,10-dimethylanthracene (1).The adduct (1) decomposed in the presence of the conjugated diene thebaine (3), to form DMA(2) and the adduct (4) of nitrosyl cyanide and thebaine.First-order kinetics, k = 6.9E-5 s-1, were observed for the release of DMA in benzene at 40 deg C, consistent with slow dissociation of the adduct (1) followed by rapid capture of nitrosyl cyanide by thebain.A similar first-order rate, k = 6.8E-5 s-1, was observed for the reaction of the adduct (1) and triphenylphosphine (2 mol equiv.) under the same conditions, the products being DMA, triphenylphosphine oxide, and triphenylphosphine N-cyanoimide (5).The reactions of nitrosyl cyanide, generated thermally from the adduct (1), were studied with a range of dienes.The conjugated dienes, N-cyanomethyl-N-northebaine (3; NCH2CN replacing NMe), trans,trans-1,4-diphenylbuta-1,3-diene (6; R=H), and ergosteryl acetate (11) all gave the expected cycloadducts (3,6-dihydro-2H-1,2-oxazines).Norbornane gave the tetracyclic adduct (10) arising from 1,4-conjugate addition of nitrosyl cyanide.The reactions of the adduct (1) with tetraphenylcyclopentadienone (14), 1,3-diphenylisobenzofuran (18), 2-methyl-1,3-diphenylisoindole (23), diazofluorene (24), and diphenyldiazomethane all took a more complex course leading in each case to the formation of an N-cyano-ketimine (alkylidene-cyanamide)
