Synthesis of Nitroalkenes
SyntheticPage 287
DOI:
Submitted: June 11, 2008, published: June 11, 2008
Authors
Ishmael Masesane (masesane@mopipi.ub.bw)
A contribution from
Chemicals
Diisopropylethylamine(Aldrich), Diethyl ether (Aldrich, Distilled from Na wire), Petroleum ether (Aldrich, distilled)
Procedure
A solution of diisopropylethylamine (5.8 g, 45mmol) in diethyl ether (10 cm3) was added dropwise to a vigorously stirred and cooled (0oC) solution of ethyl 2-iodo-3-nitropropanoate [[286|Page 286]] (10.0 g, 37 mmol) in diethyl ether (200 cm3) and the mixture was stirred for 15 min. The resulting suspension was filtered through a plug of silica. The silica was flushed with 10% diethyl ether in petroleum ether and the solvent was removed under reduced pressure to give an orange solid. The orange solid was passed through a short column of silica gel using petroleum ether/diethyl ether (9:1) as the eluent to afford title compound (4.00 g, 73 %) as a yellow solid.
Author Comments
Using this procedure, nitroacrylate could be generated in 10-20 g batches and contrary to reports that highlights the instability of nitroalkenes, ethyl (E)-3-nitroacrylate was found to be stable for months when stored in a refrigerator.
Data
m.p 36-38 oC. IR (KBr disk): 3415, 1736, 1638, 1542 cm-1; 1H NMR (200 MHz, CDCl3): 1.35 (3H, t, J = 7.0 Hz, OCH2CH3), 4.32 (2H, q, J = 7.0 Hz, OCH2CH3), 7.09 (1H, d, J = 13.6 Hz, H-2), 7.68 (1H, d, J = 13.6, H-3). 13C NMR (75 MHz, CDCl3): 13.9 (OCH2CH3), 62.4 (OCH2CH3), 127.6 (C-2), 148.9(C-3), 162.6 (C-1); MS (EI): m/z 145 (M+), 100 (100%).
Lead Reference
Bunnage, M. E., Ganesh, T., Masesane, I. B., Orton, D., Steel, P. G. Org. Lett. 2003, 5, 239-242.
Other References
McMurry, J. E.; Musser, J. H. Org. Synth. 1977, 56, 65.
Ranganathan, D.; Rao, B.; Ranganathan, S.; Mehrotra, A. K.; Iyengar, R. J. Org. Chem. 1980, 45, 1185