TY - JOUR
T1 - Acid-promoted reactions of ethyl linoleate with nitrite ions
T2 - Formation and structural characterization of isomeric nitroalkene, nitrohydroxy, and novel 3-nitro-1,5-hexadiene and 1,5-dinitro-1,3-pentadiene products
AU - Napolitano, Alessandra
AU - Camera, Emanuela
AU - Picardo, Mauro
AU - D'Ischia, Marco
PY - 2000/8/11
Y1 - 2000/8/11
N2 - The reaction of ethyl linoleate (1) with NO2
- in different air-equilibrated acidic media resulted in the formation of complex patterns of products, some of which could be isolated by repeated TLC fractionation and were formulated as the nitroalkenes 2-5, the novel (1E, 5Z)-3-nitro-1,5-hexadienes 6/7, the novel (E,E)-1,5-dinitro-1,3-pentadiene derivatives 8 and 9, and the nitro alcohols 10/11 and 12/13 by extensive GC-MS and 2D NMR analysis, as aided by 1D Hartmann-Hahn proton mapping experiments. Similar reaction of methyl oleate gave mainly nitroalkene (14/15) and allylic nitro derivatives (16/17). Formation of 2-13 may be envisaged in terms of HNO2-mediated nitration pathways in which regioisomeric β-nitroalkyl radical intermediates derived from attack of NO2 to the 1,4-pentadiene moiety of 1 evolve through competitive H-atom abstraction and free radical combination routes.
AB - The reaction of ethyl linoleate (1) with NO2
- in different air-equilibrated acidic media resulted in the formation of complex patterns of products, some of which could be isolated by repeated TLC fractionation and were formulated as the nitroalkenes 2-5, the novel (1E, 5Z)-3-nitro-1,5-hexadienes 6/7, the novel (E,E)-1,5-dinitro-1,3-pentadiene derivatives 8 and 9, and the nitro alcohols 10/11 and 12/13 by extensive GC-MS and 2D NMR analysis, as aided by 1D Hartmann-Hahn proton mapping experiments. Similar reaction of methyl oleate gave mainly nitroalkene (14/15) and allylic nitro derivatives (16/17). Formation of 2-13 may be envisaged in terms of HNO2-mediated nitration pathways in which regioisomeric β-nitroalkyl radical intermediates derived from attack of NO2 to the 1,4-pentadiene moiety of 1 evolve through competitive H-atom abstraction and free radical combination routes.
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U2 - 10.1021/jo000090q
DO - 10.1021/jo000090q
M3 - Article
C2 - 10956463
AN - SCOPUS:0034637496
VL - 65
SP - 4853
EP - 4860
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 16
ER -