10313-10-7Relevant academic research and scientific papers
Photochemical nitration by tetranitromethane. Part XLIII. Photolysis of some styrene derivatives with tetranitromethane: Mechanism of isoxazolidine formation
Eberson, Lennart,Hartshorn, Michael P.,Persson, Ola
, p. 751 - 760 (2007/10/03)
The photochemical reaction of tetranitromethane in dichloromethane or acetonitrile with 4-methylstyrene (2a), styrene (2b), 4-chlorostyrene (2c), 3-chlorostyrene (2d) or 4-acetoxystyrene (2e) gives two stereoisomeric isoxazolidines, 2-(2′-nitro-1′-X-phenyl)ethoxy-3,3-dinitro-5-(X-phenyl)isoxazolidine (3 and 4, X = 4-Me, H, 4-Cl, 3-Cl or 4-AcO), a nitro ketone, nitromethyl X-phenyl ketone (5, X = 4-Me, H, 4-Cl, 3-Cl or 4-AcO) and a nitronic ester, 3-nitro-5-(X-phenyl)-2-isoxazoline N-oxide (6, X = 4-Me, H, 4-Cl or 4-AcO). In each case, the (RS,RS)-stereoisomer 4 is the major isoxazolidine formed. The first step of the reaction is the photogeneration of the triad [2.+ NO2 (NO2)3C-]. In the formation of isoxazolidines 3 and 4, and of the nitronic esters 6, the key intermediate is assumed to be the substituted aminoxyl, 3,3-dinitro-4-(X-phenyl)isoxazolidin-N-oxyl (8, X = 4-Me, H, 4-Cl, 3-Cl or 4-AcO) formed by reaction of the substituted styrene radical cation (2.+) with trinitromethanide ion followed by cyclization of the resulting carbon radical 7. Loss of nitrogen dioxide from 8 gives nitronic esters 6, and trapping of the l-(X-phenyl)-2-nitroethyl radical, formed by addition of NO2 at the β-carbon of 2, by aminoxyl 8, gives the isoxazolidines 3 and 4 directly. Acta Chemica Scandinavica 1998.
