5
1
mmol, 1.5 eq) in diethyl ether (100 mL) placed in an ice bath and
wrapped with aluminum foil, while maintaining the temperature
below 10 °C. After 3 h at 0 °C, the mixture was kept at room
temperature in the dark until completion, was then filtered on a
celite plug and washed with 200 mL of diethyl ether. Sodium
methoxide (2.38 g, 44 mmol, 1.1 eq) in methanol (60 mL) was
added at 0 °C to the filtrate. The precipitate was collected by
filtration, washed several times with diethyl ether (5 x 10 mL).
The dried salt was dissolved in a minimum amount of water, and
acidified with the aqueous AcOH/urea at 0 °C until pH 3 (for
highly acidic substrates 2k-2l, a few drops of concentrated HCl
were then used to reach pH 1). The aci-nitro precipitate; the
slurry was kept under agitation for 15 min at 0 °C to allow the
isomerization to run to completion. The isomerization had come
to an end when the pH of the solution ceased to increase. The
precipitate was collected by filtration (or decantation for the
liquid arylnitromethanes), washed with water (2 x 10 mL) and
dried to yield the pure nitro compound (9-76 %).
White solid. Mp. 66-69 °C. H NMR δ: 5.52 (2H, s), 7.38-
ACCEPTED MANUSCRIPT
7.69 (9H, m). 13C NMR δ: 80.1, 127.2, 127.8, 128.7, 128.8,
128.9, 129.6, 130.2, 140.1, 142.3. IR (neat): 3663, 2988, 2902,
1539, 1379, 1076, 1066, 1057, 742, 712. HRMS (ESI) 214.0863
Calcd for C13H11NO2 [M+H]+: 214.0863
4.4.10. (3-methoxyphenyl)nitromethane (2j)
Yellow oil
All spectral data were in agreement with literature values3
4.4.11. (3,5-Dinitrophenyl)nitromethane (2k)
Yellow solid. Mp. 130-131 °C (lit. mp. 131-132 °C)24
All spectral data were in agreement with literature values23
4.4.12. (2,4-Dinitrophenyl)nitromethane (2l)
Yellow solid. Mp. 140-141 °C (lit. mp. 141-142 °C)25
All spectral data were in agreement with literature values25
4.4.13. 2-Nitro-5-nitromethylfuran (2m)
The first ethereal filtrate could be evaporated to dryness and
taken up with some water to precipitate the essentially pure
benzyl alcohol.
1
Red oil. H NMR δ: 5.57 (2H, s), 6.87 (1H, d, J = 3.6 Hz),
7.35 (1H, d, J = 3.6 Hz). 13C NMR δ: 70.2, 111.4, 116.2, 144.7.
HRMS (ESI) 173.0192 Calcd for C5H4N2O5 [M+H]+: 173.0193
4.4.1. (2-Nitrophenyl)nitromethane (2a)
Yellow solid. Mp. 59-60 °C (lit. mp. 60-62 °C)1
Acknowledgments
All spectral data were in agreement with literature values3
We thank Direction Générale de l'Armement (DGA) for the
financial support of this study.
4.4.2. Phenylnitromethane (2b)
Yellowish liquid
References and notes
All spectral data were in agreement with literature values3
1. R. Walvoord, M. Kozlowski, J. Org. Chem., 2013, 78, 8859-8864
2. V. Meyer, Liebigs Ann. Chem., 1874, 171, 1-56
3. R. Walvoord, S. Beritt, M. Kozlowski, Org. Lett., 2012, 14, 4086-
4089
4. N. Kornblum, R. Smiley, R. Blackwood, D. Iffland, J. Am. Chem.
Soc., 1955, 77, 6269-6280
5. N. Kornblum, H. Larson, R. Blackwood, D. Mooberry, E. Oliveto,
G. Graham, J. Am. Chem. Soc., 1956, 78, 1497-1500
6. N. Kornblum, W. Weaver, J. Am. Chem. Soc, 1958, 80, 4333-4337
7. A. Tishov, U. Schmidhammer, S; Roth, E. Riele, H. Mayr, Angew.
Chem. Int., 2005, 44, 4623; H. Mayr, M. Breugst, A. Ofial,
Angew. Chem. Int., 2011, 50, 6470-6505
8. R. Ballini, L. Barboni, G. Giarlo, J. Org. Chem., 2004, 69, 6907-
6908
9. A. Baruah, B. Kalita, N. Barua, Synlett, 2000, 7, 1064-1066
10. M. Makosza, M. Barbasiewicz, K. Wojciechowski, Synlett, 2001,
7, 1121-1122
4.4.3. (3-Nitrophenyl)nitromethane (2c)
Yellow solid. Mp. 94-95 °C (lit. mp. 94-95 °C)19
All spectral data were in agreement with literature values19
4.4.4. (4-Nitrophenyl)nitromethane (2d)
Yellow solid. Mp. 90-91 °C (lit. mp. 90-91 °C)19
All spectral data were in agreement with literature values19
4.4.5. (2-Bromophenyl)nitromethane (2e)
Orange oil. 1H NMR δ: 5.60 (2H, s), 7.29 (1H, dd, J = 1.6, 7.7
Hz), 7.39 (1H, dt, J = 1.6, 16.1 Hz), 7.29 (1H, dt, J = 1.6, 16.1
Hz), 7.63 (1H, d, J = 7.7 Hz). 13C NMR δ: 79.1, 125.8, 128.1,
129.5, 131.8, 132.9, 133.3. IR (neat): 1551, 1444, 1425, 1368,
1317, 1029, 735. HRMS (ESI) 215.9655 Calcd for C7H6BrNO2
[M+H]+: 215.9655
11. M. Meciarova, S. Toma, P. Babiak, Chem. Pap., 2004, 58, 104-
108
12. A. Black, F. Babers, Org. Synth., 1939, 19, 73-76
13. P. Butler, B. Golding, G. Laval, H. Loghmani-Khouzani, R.
Ranjbar-Karimi, M. Sadeghi, Tetrahedron, 2007, 63, 11160-11166
14. H. Feuer, J. Lawrence, J. Org. Chem., 1972, 37, 3662-3670
15. T. Bug, T. Lemek, H. Mayr, J. Org. Chem., 2004, 69, 7565-7576
16. H. Pinnick, The Nef Reaction, Org. Reactions, 2004, 38, 655-792
17. N. Kornblum, G. E. Grahm, J. Am. Chem. Soc., 1951, 73, 4041-
4043
4.4.6. (2-Fluorophenyl)nitromethane (2f)
Yellow oil. 1H NMR δ: 5.55 (2H, s), 7.17-7.29 (2H, m), 7.42-
7.52 (2H, m). 13C NMR δ: 72.9, 115.9, 117.1, 124.6, 132.3,
160.1, 162.6. IR (neat): 2988, 2902, 1550, 1495, 1373, 1240,
1057, 758, 740. HRMS (ESI) 156.0455 Calcd for C7H6FNO2
[M+H]+: 156.0455
18. A. Metz, M. Kozlowski, J. Org. Chem., 2013, 78, 717-722
19. K. Ando, Y. Shimazu, N. Seki, H. Yamataka, J. Org. Chem.,
2011, 76, 3937-3945
4.4.7. 1-Nitromethyl-4-trifluoromethylbenzene (2g)
Yellow solid. Mp. 40-41 °C (lit. mp. 41-42 °C)19
20. We used 20 mol% of tetrabutylammonium iodide in the silver
nitrite slurry
All spectral data were in agreement with literature values3
21. We used 20 mol% of sodium iodide in the silver nitrite slurry
22. T. Phan, H. Mayr, Eur. J. Org. Chem., 2006, 11, 2530-2537
23. J. Gandler, O. Saunders, R. Barbosa, J. Org. Chem., 1997, 62,
4677-4682
24. L. Fieser, M. Gates, J. Am. Chem. Soc., 1946, 68, 2249-2252
25. T. Kawakami, H. Suzuki, Tetrahedron Lett., 1999, 40, 1157-1160
4.4.8. (4-Cyanophenyl)nitromethane (2h)
Yellowish solid. Mp. 75-76 °C (lit. mp. 95-96 °C)22
All spectral data were in agreement with literature values22
4.4.9. 1-Nitromethyl-3-phenylbenzene (2i)