d The reaction was performed under refluxing 1,2-dichloroethane with
diamines (2.0 mmol) and m-CPBA (16.0 mmol) for 10 h.
e ND: not determined, NR: no reaction.
removed under reduced pressure and the residue was treated
with 10% NaOH solution followed by extraction with EtOAc.
The combined extracts were washed with H2O and brine, dried
over anhydrous Na2SO4. Removal of the solvent under vacuum
afforded the crude product, which was purified by column
chromatography using hexane/ethyl acetate as eluant.
In conclusion, an efficient and practical method for the
synthesis of nitroarenes from aromatic amines using
commercially available reagents m-CPBA was developed.
The investigation of the profile of substrates was well
demonstrated. The described chemistry expands the repertoire
of reactions carried out by m-CPBA, a versatile oxidant with
ever-increasing utility in chemical synthesis.
1
Nitrobenzene (2a)[8a]. Yellow oil, yield 81%; H NMR (400
MHz, CDCl3): δ = 8.24 (d, J = 8.3 Hz, 2H), 7.71 (t, J = 7.4 Hz,
1H), 7.56 (t, J = 7.9 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ =
148.2, 134.6, 129.3, 123.5; GC-MS (m/z) [M]+: 123 (C6H5NO2,
123.03).
4-Nitroanisile (2b)[8b]. White solid, yield 95%; mp 50-51 oC; 1H
NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 9.0 Hz, 2H), 6.96 (d, J
= 9.0 Hz, 2H), 3.91 (s, 3H); 13C NMR (100 MHz, CDCl3): δ =
164.6, 141.5, 125.9, 114.0, 55.9; GC-MS (m/z) [M]+: 153
(C7H7NO3, 153.04).
Acknowledgments
We are grateful for financial support from The
Fundamental Research Funds for the Central Universities
(WY1113007).
4-Nitrochlorobenzene (2c)[8b]. Yellow solid, yield 85%; mp 81-
83 oC; 1H NMR (400 MHz, CDCl3): δ = 8.21-8.17 (m, 2H),
7.54-7.27 (m, 2H); 13C NMR (100 MHz, CDCl3): δ = 146.5,
141.4, 129.6, 124.9; MS (EI) m/z: 157 (100%), 159 (34%) [M] +.
References and notes
o
4-Nitrotoluene (2d)[8a]. Yellow solid, yield 85%; mp 52-53 C;
1H NMR (400 MHz, CDCl3): δ = 8.12 (d, J = 8.7 Hz, 2H), 7.32
(d, J = 8.3 Hz, 2H), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ = 146.2, 145.9, 129.8, 123.5, 21.6; MS (EI) m/z: 91 (100%),
137 (95%) [M]+.
1. Ono, N. The Nitro Group in Organic Synthesis; Wiley-VCH:
New York, 2001.
2. (a) Batcho, A. D.; Leimgruber, W. Org. Synth. 1985, 63, 214-
220; (b) Clark, R. D.; Repke, D. B. Heterocycles 1984, 22, 195-
221; (c) Bartoli, G.; Palmieri, G.; Bosco, M.; Dalpozzo,
R. Tetrahedron Lett. 1989, 30, 2129-2132; (d) Dalpozzo, R.;
Bartoli, G. Curr. Org. Chem. 2005, 9, 163-178.
3. Baeyer, A. V.; Drewsen, V. Berichte der deutschen chemischen
Gesellschaft. 1882, 15, 2856-2864.
4. Olah, G. A.; Malhotra, R.; Narang, S. C. Nitration: Methods and
Mechanism, VCH, New York, 1989.
2-Nitrochlorobenzene (2e)[8c]. Yellow liquid, yield 78%; 1H
NMR (400 MHz, CDCl3): δ = 7.88 (dd, J1 = 8.1 Hz, J2 = 1.4 Hz,
1H), 7.57-7.52 (m, 2H), 7.44-7.42 (m, 1H); 3C NMR (100 MHz,
CDCl3): δ = 148.1, 133.2, 131.9, 127.6, 127.0, 125.6; MS (EI)
m/z: 111 (75%), 157 (100%), 159 (33%) [M] +.
3-Nitrochlorobenzene (2f)[8a]. Light yellow solid, yield 81%;
mp 45-46 oC; 1H NMR (400 MHz, CDCl3): δ = 8.24 (t, J = 2.1
Hz, 1H), 8.14 (ddd, J1 = 8.3 Hz, J2 = 2.1 Hz, J3 = 1.0 Hz, 1H),
7.69 (ddd, J1 = 8.0 Hz, J2 = 2.0 Hz, J3 = 1.0 Hz, 1H), 7.51 (t, J =
8.1 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ = 148.8, 135.4,
134.7, 130.4, 123.9, 121.7; GC-MS (m/z) [M]+: 157
(C6H4ClNO2, 156.99).
5. (a) Feuer, H.; Nielson, A. T. Nitro Compounds: Recent
Advances in Synthesis and Chemistry; VCH: New York, 1990;
(b) Torssell, K. B. G. Nitrile Oxides, Nitrones, and Nitronates in
Organic Synthesis: Novel Strategies inSynthesis; VCH: New
York, 1988; (c) Schofield, K. Aromatic Nitrations; Cambridge
University Press: Cambridge, 1980.
6. (a) Emmons, W. D.; Ferris, F. J. Am. Chem. Soc. 1953, 75,
4623-4624; (b) Murray, R. W.; Rajadhyaksha, S. N.; Mohan, L.
J. Org. Chem., 1989, 54, 5783-5788; (c) Webb, K. S.;
Seneviratne, V. Tetrahedron Letters, 1995, 36, 2377-2379; (d)
Das, S. S.; Nath, U.; Deb, D.; Das, P. J. Syn. Commun. 2004, 34,
2359-2363; (e) Reddy, K. R.; Maheswari, C. U.; Venkateshwar,
M.; Kantam, M. L. Adv. Synth. Catal., 2009, 351, 93-96; (f)
Ratnikov, M. O.; Farkas, L. E.; McLaughlin, E. C.; Chiou, G.;
Choi, H.; El-Khalafy, S. H.; Doyle, M. P. J. Org. Chem. 2011,
76, 2585-2593.
7. (a) Robinson, C. H.; Milewich, L.; Hofer, P. J. Org. Chem. 1963,
31, 524-528; (b) Beckett, A. H.; Jones, G. R.; Coutts, R. T.
Tetrahedron 1976, 32, 1267-1276; (c) Gilbert, K. E.; Borden, W.
T. J. Org. Chem. 1979, 44, 659-661; (d) Kimmel, E. C.; Casida, J.
E.; Ruzo, L. O. J. Agric. Food Chem. 1986, 34, 157-161; (e)
Schwertfeger, H.; Würtele, C.; Schreiner, P. R. Synlett 2010, 3,
493-495.
1,4-Dinitrobenzene (2g). Yellow solid, yield 80%; mp 165-166
1
oC; H NMR (400 MHz, CDCl3): δ = 8.44 (s, 4H); 13C NMR
(100 MHz, CDCl3): δ = 151.1, 124.9; MS (EI) m/z: 168 (100%)
[M] +.
1-Bromo-2-nitrobenzene (2h)[8c]. Yellow solid, yield 74%; mp
o
43-45 C; 1H NMR (400 MHz, CDCl3): δ = 7.86-7.83 (m, 1H),
7.76-7.74 (m, 1H), 7.49-7.42 (m, 2H); 13C NMR (100 MHz,
CDCl3): δ = 149.9, 135.1, 133.2, 128.3, 125.6, 114.5; GC-MS
(m/z) [M]+: 201 (C7H7NO3, 200.94); MS (EI) m/z: 155 (79%),
157 (79%), 201 (100%), 203 (100%) [M] +.
1-Nitronaphthalene (2i). Yellow solid, yield 58%; mp 55-57
oC; 1H NMR (400 MHz, CDCl3): δ = 8.55 (d, J = 8.7 Hz, 1H),
8.22 (dd, J1 = 7.6 Hz, J2 = 1.1 Hz, 1H), 8.11 (d, J = 8.2 Hz, 1H),
7.95 (d, J = 8.2 Hz, 1H), 7.71 (ddd, J1 = 8.6 Hz, J2 = 7.0 Hz, J3 =
1.3 Hz, 1H), 7.63-7.60 (m, 1H), 7.53 (dt, J1 = 7.9 Hz, J2 = 1.2
Hz, 1H); 13C NMR (100 MHz, CDCl3): δ = 146.6, 134.7, 134.4,
129.5, 128.6, 127.4, 125.1, 124.1, 124.0, 123.1; MS (EI) m/z:
127 (94%), 173 (100%) [M] +.
1,3,5-Trimethyl-2-nitrobenzene (2k)[8d]
. Pale yellow solid,
8. (a) Yang, H.; Li, Y.; Jiang, M.; Wang, J. M.; Fu, H. Chem. Eur. J.
2011,
yield 61%; mp 43-45 oC; 1H NMR (400 MHz, CDCl3): δ = 6.92
(s, 2H), 2.31 (s, 3H), 2.28 (s, 6H); 13C NMR (100 MHz, CDCl3):
δ = 149.8, 140.3, 129.6, 129.4, 21.0, 17.5; MS (EI) m/z: 148
(100%), 165(62%) [M] +.
17, 5652-5660; (b) Aridoss, G.; Laali, K. K. J. Org.
Chem. 2011, 76, 8088-8094; (c) Shi, M;. Cui, S. C. Adv. Synth.
Catal. 2003, 345, 1329-1333; (d) Förster, S.; Rieker, A. J. Org.
Chem. 1996, 61, 3320-3326; (e) Schlosser, M.; Ginanneschi, A.;
Leroux, F. Eur. J. Org. Chem. 2006, 13, 2956-2969; (f) Roice,
M.; Christensen, S. F.; Meldal, M. Chem. Eur. J. 2004, 10, 4407-
4415; (g) Zhang, J. T.; Zhang, Z. H.; Wang, Y.; Zheng, X. Q.;
Wang, Z. Y. Eur. J. Org. Chem. 2008, 30, 5112-5116.
2,6-Dinitrotoluene (2l). Pale yellow solid, yield 63%; mp 65-66
1
oC; H NMR (400 MHz, CDCl3): δ = 8.00 (d, J = 8.1 Hz, 2H),
7.53 (t, J = 8.1 Hz, 1H), 2.59 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ = 151.7, 127.5, 127.5, 127.3, 14.8; MS (EI) m/z: 165
(100%), 182 (3%) [M] +.
9. General procedure for the oxidation of aromatic amines with m-
CPBA: m-CPBA (1.7 g, 8.0 mmol, 85%) was dissolved in 1,2-
dichloroethane (15.0 mL) in a three-neck flask equipped with a
condenser and heated to reflux (at r.t. in case of 1b). Then, the
substrate aromatic amine (2.0 mmol) dissolved in 1,2-
dichloroethane (5.0 mL) was added dropwise to the refluxing
peracid solution. After 10 h, the mixture was cooled to r.t. and
quenched with saturated aqueous Na2S2O3. The solvent was
2-Bromo-4-fluoro-1-nitrobenzene (2m)[8e]. Yellow solid, yield
o
1
71%; mp 42-43 C; H NMR (400 MHz, CDCl3): δ = 7.97 (dd,
J1 = 9.1 Hz, J2 = 5.2 Hz, 1H), 7.49 (dd, J1 = 7.8 Hz, J2 = 2.7 Hz,
1H), 7.18 (ddd, J1 = 9.1 Hz, J2 = 7.2 Hz, J3 = 2.7 Hz, 1H); 13C
1
NMR (100 MHz, CDCl3): δ = 163.7 (d, JCF = 260 Hz), 146.1,
127.9 (d, 3JCF = 10 Hz), 122.5 (d, 2JCF = 26 Hz), 116.4 (d, 3JCF
=
2
11 Hz), 115.5 (d, JCF = 23 Hz); 19F (376 MHz, CDCl3): δ = -