LETTER
Preparation of Monobromo and Bromoiodo Hydroxy Pyridines
(10) For bromopyridines see: (a) Bonnet, V.; Mongin, F.;
1681
References
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(14) Unpublished results. Bromination of methyl hydroxy-
pyridines 3–6 were carried out with 1 equivalent of NBS in
acetonitrile. For 3, 3-bromo-, 5-bromo- and 3,5-dibromo 2-
hydroxy-6-methyl pyridines were formed in a 28:54:9 ratio.
For 4, 3-bromo-, 5-bromo- and 3,5-dibromo 2-hydroxy-4-
methyl pyridines were formed in a 36:44:8 ratio. For 5, 6-
bromo- and 4,6-dibromo 3-hydroxy-2-methyl pyridines
were formed in a 20:40 ratio. For 6 2-bromo- and 2,4-
dibromo 3-hydroxy-6-methyl pyridines were formed in a
23:38 ratio. The rest up to 100% were unaltered starting
material.
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(8) For RMgX see: (a) Bérillon, L.; Leprête, A.; Turck, A.; Plé,
N.; Quéguiner, G.; Cahiez, G.; Knochel, P. Synlett 1998,
1359. (b) Trécourt, F.; Breton, G.; Bonnet, V.; Mongin, F.;
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2002, 4181.
(15) Dibromopyridines 9–12 were characterized on the basis of
their 1H NMR (d in ppm, DMSO-d6, 300 MHz) and 13
C
NMR (d in ppm, DMSO-d6, 75 MHz) spectroscopic data and
elemental analysis.
Compound 9: white solid; mp 223–224 °C (Et2O/hexane);
1H NMR: 2.23 (s, 3 H, CH3), 8.04 (s, 1 H, H-C4), 12.50 (br
s, 1 H, OH); 13C NMR: 19.2 (CH3), 97.0 (C-5), 112.3 (C-3),
144.8 (C-4), 145.7 (C-6), 158.3 (C-2); Anal. Calcd for
C6H5NOBr2: C, 27.00; H, 1.89; N, 5.25. Found: C, 27.44; H,
1.98; N, 5.29.
Compound 10: white solid; mp 222–223 °C (methanol); 1H
NMR: 2.41 (s, 3 H, CH3), 7.76 (s, 1 H, H-C6), 12.29 (br s, 1
H, OH); 13C NMR: 24.1 (CH3), 100.5 (C-5), 116.7 (C-3),
135.0 (C-6), 149.3 (C-4), 157.7 (C-2); Anal. Calcd. for
C6H5NOBr2: C, 27.00; H, 1.89; N, 5.25. Found: C, 27.08; H,
1.95; N, 5.37.
Compound 11: yellow solid; mp 107–108 °C (Et2O/hexane);
1H NMR: 2.39 (s, 3 H, CH3), 7.68 (s, 1 H, H-C5), 9.98 (br s,
1 H, OH); 13C NMR: 19.9 (CH3), 122.4 (C-4), 128.4 (C-5),
128.6 (C-6), 148.8 and 149.1 (C-2 and C-3); Anal. Calcd for
C6H5NOBr2: C, 27.00; H, 1.89; N, 5.25. Found: C, 27.24; H,
2.02; N, 5.34.
(9) (a) Skerlj, R. T.; Bogucki, D.; Bridger, G. J. Synlett 2000,
1488. (b) Cherng, Y.-J. Tetrahedron 2002, 58, 4931.
Compound 12: yellow solid; mp 100–101°C (Et2O/hexane);
1H NMR (DMSO-d6): 2.33 (s, 3 H, CH3), 7.52 (s, 1 H, H-
C5), 10.30 (br s, 1 H, OH); 13C NMR (DMSO-d6): 22.2
(CH3), 121.9 (C-4), 127.2 (C-5), 131.3 (C-2), 146.3 (C-6),
150.6 (C-3). Anal. Calcd for C6H5NOBr2: C, 27.00; H, 1.89;
N, 5.25. Found: C, 27.44; H, 2.03; N, 5.34.
(16) Mongin, F.; Fourquez, J.-M.; Rault, S.; Levacher, V.;
Godard, A.; Trécourt, F.; Quéguiner, G. Tetrahedron Lett.
1995, 36, 8415.
Synlett 2003, No. 11, 1678–1682 © Thieme Stuttgart · New York