3-Acetyl-5-nitropyridine (6g). White prisms (20%); 1H
NMR: dH (300 MHz; CDCl3; Me4Si) 2.76 (s, 3H), 8.97 (t,
J = 2.4 Hz, 1H), 9.44 (d, J = 2.4 Hz, 1H), 9.60 (d, J = 2.4 Hz,
1H); 13C NMR: dC 27.0, 130.3, 132.4, 144.3, 148.1, 154.2, 194.3.
Anal. (Found: C, 50.67; H, 3.53; N, 16.84. Calc for C7H6N2O3:
C, 50.61; H, 3.64; N, 16.87%).
References
1 F. Friedl, Chem. Ber., 1912, 45, 428.
2 J. M. Bakke, Pure Appl. Chem., 2003, 75, 1403.
3 J. M. Bakke, H. S. H. Gautun, C. Rømming and I. Sletvold,
ARKIVOC, 2001, x, 26.
4 J. Chen, G. Ling and S. Lu, Tetrahedron, 2003, 59, 8251.
5 D. L. Romero, R. A. Morge, C. Biles, N. Berrios-Pen˜a, P. D. May,
J. R. Palmer, P. D. Johnson, H. W. Smith, M. Busso, C.-K. Tan, R. L.
Voorman, F. Reusser, I. W. Althaus, K. M. Downey, A. G. So, L.
Resnick, W. G. Tarpley and P. A. Aristoff, J. Med. Chem., 1994, 37,
999.
6 R. W. Millar, R. P. Claridge, J. P. B. Sandall and C. Thompson,
ARKIVOC, 2002, iii, 19.
7 S. Youssif, ARKIVOC, 2001, i, 242.
1
4-Acetyl-5-nitropyridine (6h). Yellow oil (83%); H NMR:
dH (300 MHz; CDCl3; Me4Si) 2.60 (s, 3H), 7.36 (dd, J = 4.9,
0.7 Hz, 1H), 8.97 (dd, J = 4.9, 0.7 Hz, 1H), 9.37 (s, 1H); 13C
NMR: dC 29.9, 120.6, 144.7, 145.7, 150.9, 155.1, 197.8. Anal.
(Found: C, 50.67; H, 3.52; N, 16.74. Calcd. for C7H6N2O3: C,
50.61; H, 3.64; N, 16.87%).
2-Fluoro-5-nitropyridine (6i). Yellow oil (10%); 1H NMR: dH
(300 MHz; CDCl3; Me4Si) 7.14 (ddd, J = 8.9, 3.2, 0.6 Hz, 1H),
8.62 (ddd, J = 8.9, 6.4, 2.9 Hz, 1H), 9.15 (ddd, J = 2.9, 1.1,
8 A. R. Katritzky and B. J. Ridgewell, J. Chem. Soc., 1963, 3882.
9 C. D. Johnson, A. R. Katritzky, B. J. Ridgewell and M. Viney,
J. Chem. Soc. B, 1967, 1204.
10 C. D. Johnson, A. R. Katritzky, N. Shakir and M. Viney, J. Chem.
Soc. B, 1967, 1213.
11 A. R. Katritzky, B. Terem and E. V. Scriven, J. Chem. Soc., Perkin
Trans. 2, 1975, 1600.
12 A. R. Katritzky and W.-Q. Fan, Heterocycles, 1992, 34, 2179.
13 A. R. Katritzky and C. D. Johnson, Angew. Chem., Int. Ed. Engl.,
1967, 6, 608.
0.6 Hz, 1H); 13C NMR: dC 110.5 (JCF = 16.6 Hz), 136.8 (JCF
=
10.6 Hz), 142.6, 144.8 (JCF = 17.4 Hz), 165.7 (JCF = 249.7 Hz).
3-Chloro-5-nitropyridine (6j). White prisms (76%); 1H
NMR: dH (300 MHz; CDCl3; Me4Si) 8.50 (t, J = 1.7 Hz, 1H),
8.89 (d, J = 1.7 Hz, 1H), 9.34 (d, J = 1.7 Hz, 1H); 13C NMR:
dC 130.8, 132.5, 142.7, 144.2, 154.0. Anal. (Found: C, 38.33; H,
1.87; N, 17.39. Calcd. for C5H3ClN2O2: C, 37.89; H, 1.91; N,
17.68%).
14 A. R. Katritzky and M. Kingsland, J. Chem. Soc. B, 1968, 862.
15 P. J. Brignell, A. R. Katritzky and H. O. Tarhan, J. Chem. Soc. B,
1968, 1477.
16 A. R. Katritzky, H. O. Tarhan and S. Tarhan, J. Chem. Soc. B, 1970,
1
114.
4-Nitroisoquinoline (6k). Orange needles (37%); H NMR:
17 A. G. Burton, P. J. Halls and A. R. Katritzky, J. Chem. Soc., Perkin
Trans. 2, 1972, 1953.
18 A. G. Burton, R. D. Frampton, C. D. Johnson and A. R. Katritzky,
J. Chem. Soc., Perkin Trans. 2, 1972, 1940.
19 G. Bianchi, A. G. Burton, C. D. Johnson and A. R. Katritzky,
J. Chem. Soc., Perkin Trans. 2, 1972, 1950.
20 J. M. Bakke, I. Hegbom, E. Øvereeide and K. Aaby, Acta Chem.
Scand., 1994, 48, 1001.
21 T. Mori and H. Suzuki, Synlett, 1995, 383.
22 H. Suzuki, M. Iwaya and T. Mori, Tetrahedron Lett., 1997, 38,
5647.
23 R. Murugan, E. F. V. Scriven, G. F. Hillstrom and P. K. Ghoshal,
Int. Patent WO 2002090328, 2002; R. Murugan, E. F. V. Scriven,
G. F. Hillstrom and P. K. Ghoshal, Chem. Abstr., 2002, 137,
352895.
dH (300 MHz; CDCl3; Me4Si) 7.79 (ddd, J = 8.1, 7.8, 1.0 Hz,
1H), 7.96 (ddd, J = 8.1, 8.1, 1.4 Hz, 1H), 8.13 (dddd, J = 8.1,
1.4, 0.7, 0.5 Hz, 1H), 8.62 (ddd, J = 8.7, 1.0, 0.7 Hz, 1H), 9.26
(s, 1H), 9.43 (d, J = 0.8 Hz, 1H); 13C NMR: dC 122.5, 127.8,
128.4, 128.9, 129.0, 134.0, 141.1, 158.0. Anal. (Found: C, 62.03;
H, 3.41; N, 15.96. Calcd. for C9H6N2O2: C, 62.05; H, 3.47; N,
16.08%).
3-Nitro-4-(N,N-dimethylamino)pyridine (6l). Yellow micro-
crystals (32%); 1H NMR: dH (300 MHz; CDCl3; Me4Si) 3.00 (s,
6H), 6.79 (d, J = 6.2 Hz, 1H), 8.27 (d, J = 6.2 Hz, 1H), 8.77 (s,
1H). 13C NMR: dC 41.5, 110.6, 148.0, 149.1, 151.3, 153.0. Anal.
(Found: C, 50.25; H, 5.40; N, 24.95. Calcd. for C7H9N3O2: C,
50.28; H, 5.43; N, 25.14%).
2,4-Dimethyl-5-nitropyridine (6m). Yellow oil (52%); 1H
NMR: dH (300 MHz; CDCl3; Me4Si) 2.61 (s, 3H), 2.63 (s, 3H),
7.26 (br s, 1H), 9.10 (s, 1H); 13C NMR: dC 20.2, 24.3, 126.6,
143.2, 143.8, 145.7, 163.3. Anal. (Found: C, 55.46; H, 5.35; N,
18.24. Calcd. for C7H8N2O2: C, 55.24; H, 5.30; N, 18.41%).
24 Y. Ito, Y. Hamada and M. Hirota, Chem. Pharm. Bull., 1972, 20,
2678.
25 M. E. Kurz, L. T. A. Yang, E. P. Zahora and R. C. Adams, J. Org.
Chem., 1973, 38, 2271.
26 V. Gold, E. D. Hughes and C. K. Ingold, J. Chem. Soc., 1950,
2467.
27 F. Francis, Chem. Ber., 1906, 39, 3798.
28 J. M. Bakke and J. Riha, Acta. Chem. Scand., 1999, 53, 356.
29 Y. Tohda, M. Eiraku, T. Nakagawa, Y. Usami, M. Ariga, T.
Kawashima, K. Tani, H. Watanabe and Y. Mori, Bull. Chem. Soc.
Jpn., 1990, 63, 2820.
1
3,4-Dimethyl-5-nitropyridine (6n). Yellow prisms (30%); H
NMR: dH (300 MHz; CDCl3; Me4Si) 2.39 (s, 3H), 2.47 (s, 3H),
8.54 (s, 1H), 8.87 (s, 1H); 13C NMR: dC 15.0, 17.0, 134.2, 140.2,
143.1, 153.1, 166.7. Anal. (Found C, 55.54; H, 5.34; N, 18.29.
Calcd. for C7H8N2O2: C, 55.24; H, 5.30; N, 18.41%).
30 J. M. Bakke and E. Ranes, Synthesis, 1997, 281.
31 M.-C. Liu, T.-S. Lin and A. C. Sartorelli, Synth. Commun., 1990, 20,
2965.
32 J. M. Bakke, E. Ranes, J. Riha and H. Svensen, Acta Chem. Scand.,
5-Methyl-2-(trinitromethyl)pyridine (6oꢀ). White prisms
(10%); H NMR: dH (300 MHz; CDCl3; Me4Si) 2.50 (s, 3H),
7.78 (dd, J = 8.2, 1.4 Hz, 1H), 7.89 (d, J = 8.2 Hz, 1H), 8.59
(br s, 1H); 13C NMR: dC 18.6, 124.5, 127.8, 138.0, 139.1, 139.8,
150.8. The structure of 6oꢀ was determined by X-ray analysis.‡
1999, 53, 141.
1
33 Y. Uchibori, M. Umeno and H. Yoshioka, Heterocycles, 1992, 34,
1507.
34 J. H. Clark and D. J. Macquarrie, Tetrahedron Lett., 1987, 28, 111.
35 SHELXTL6, Bruker-AXS, Madison, Wisconsin, USA, 2000.
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 5 3 8 – 5 4 1
5 4 1