A. S. Voisin et al. / Tetrahedron 61 (2005) 1417–1421
1421
1616–1617. (b) Rozen, S.; Hebel, D. Heterocycles 1989, 28,
249–258.
3.5. General procedure for synthesis of halohydroxy-
pyridine-N-oxides in anhydrous conditions (21)
13. Nasreen, A.; Adapa, S. R. Heterocycl. Commun. 2001, 7,
501–506.
To a stirred suspension of boronic acid (0.5 g) in 25 mL of
chloroform was slowly added meta-chloroperbenzoic acid
(2.4 equiv). The reaction was refluxed for 5 h. The mixture
was allowed to warm to room temperature. The resulting
suspension was washed with 25 mL of sodium hydrogen
carbonate. The organic layer was collected, dried over
calcium chloride/magnesium sulfate mixture, filtrated and
concentrated to dryness. Recrystallization from diethylether
gave pure halohydroxypyridine-N-oxides.
14. Some protected 3-hydroxypyridines have been functionalized
by halogen–metal exchange, see: Lin, N. H.; Gunn, D. E.; Li,
Y.; He, Y.; Bai, H.; Ryther, K. B.; Kuntzweiler, T.; Donnelly-
Roberts, D. L.; Anderson, D. J.; Campbell, J. E.; Sullivan, J. P.;
Arneric, S. P.; Holladay, M. W. Bioorg. Med. Chem. Lett.
1998, 8, 249–254 and references cited herein.
15. Various oxidants have been used: hydrogen peroxide, see:
Brown, H. C.; Subba Rao, B. C. J. Org. Chem. 1957, 22,
1137–1138. Organic peroxides, see: Shushunov, V. A.;
Maslennikov, V. P.; Makin, G. I.; Kulakov, S. I. Zh. Org.
Khim. 1972, 8, 1409–1412. Oxonew, see: Webb, S. K.; Levy,
D. Tetrahedron Lett. 1995, 36, 5117–5118.
3.5.1. 3-Bromo-5-hydroxypyridine-N-oxide (21). Beige
solid, mp 208 8C. IR (KBr): 3109, 2477, 1563, 1445, 1320,
1226, 1151, 1004, 910, 845, 666, 595 cmK1. 1H NMR (d6-
DMSO) d 11.06 (bs, 1H), 7.99 (s, 1H), 7.76 (s, 1H), 6.93 (s,
1H). 13C NMR (d6-DMSO) d 155.9, 131.9, 129.9, 127.1,
114.0. Anal. Calcd for C5H4BrNO2: C, 31.61; H, 2.12; N,
7.37. Found: C, 31.68; H, 2.11; N, 7.21.
`
16. Matondo, H.; Souirti, S.; Baboulene, M. Synth. Commun.
2003, 33, 795–800.
17. Matondo, H.; Ouhaja, N.; Souirti, S.; Baboulene, M. Main
Group Met. Chem. 2002, 25(3), 163–167.
`
18. (a) Bouillon, A.; Lancelot, J. C.; Collot, V.; Bovy, P. R.; Rault,
S. Tetrahedron 2002, 58, 2885–2890; (b) Sopkova-de Oliveira
Santos, J.; Bouillon, A.; Lancelot, J. C.; Rault, S. Acta
Crystallogr., Sect. C: Cryst. Struct. Commun. 2003, C58,
o111–o113.
Acknowledgements
´
The authors thank Laboratoires Servier, Conseil Regional
´
de Basse-Normandie and FEDER (Fonds Europeens de
Developpement Economique Regional) for their financial
19. Bouillon, A.; Lancelot, J. C.; Collot, V.; Bovy, P. R.; Rault, S.
Tetrahedron 2002, 58, 3323–3328.
´
´
support.
20. Bouillon, A.; Lancelot, J. C.; Collot, V.; Bovy, P. R.; Rault, S.
Tetrahedron 2002, 58, 4369–4373.
21. (a) Bouillon, A.; Lancelot, J. C.; Sopkova-de Oliveira Santos,
J.; Collot, V.; Bovy, P. R.; Rault, S. Tetrahedron 2003, 59,
10043–10049. (b) Sopkova-de Oliveira Santos, J.; Bouillon,
A.; Lancelot, J. C.; Rault, S. Acta Crystallogr., Sect. C: Cryst.
Struct. Commun. 2003, C59, o596–o597.
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