4
46
Can. J. Chem. Vol. 87, 2009
5
-Bromo-2-hydroxybenzaldehyde
00397910008087387.; (c) Oberhauser, T. J. Org. Chem.
1
997, 62, 4504. doi:10.1021/jo9622993.
White solid. R : 0.37 (20% EtOAc/hexanes on silica). The
f
(
(
(
7) Auerbach, J.; Weissman, S. A.; Blacklock, T. J.; Angeles, M.
R.; Hoogsteen, K. Tetrahedron Lett. 1993, 34, 931. doi:10.
1016/S0040-4039(00)77457-0.
8) This method affords predominantly orthobrominated arenes:
Fujisaki, S.; Nishida, A. Bull. Chem. Soc. Jpn. 1993, 66,
product was purified via flash chromatography (20% EtOAc/
hexanes on silica). Yield: 18%, mp 102–105 8C (lit.
mp 104–105 8C). H NMR (300 MHz, CDCl ) d: 10.92 (s,
5
0
1
3
1
9
H), 9.83 (s, 1H), 7.65 (d, J = 2.4 Hz, 1H), 7.58 (dd, J = 2.7,
.0 Hz, 1H), 6.89 (d, J = 9.0 Hz, 1H). C NMR (75 MHz,
1
3
1
576. doi:10.1246/bcsj.66.1576.
9) (a) Bromination in CCl4: Djerassi, C. Chem. Rev. 1948, 43,
71 doi:10.1021/cr60135a004. PMID:18887958.; (b) Bromi-
CDCl ) d: 196.1, 161.3, 140.5, 136.4, 122.5, 120.6, 112.1.
3
+
1
13
GC-MS (5.53) [M] : 200.0. H NMR and C NMR spectra
are in agreement with those previously reported.
2
5
0,51
nation in CH2Cl2: Mistry, A. G.; Smith, K.; Bye, M. R. Tet-
rahedron Lett. 1986, 27, 1051 doi:10.1016/S0040-4039(86)
4
-Bromo-3,5-dimethyl-N,N-dimethylaniline
Isolated as a thick colorless oil that solidified to a crystal-
line white substance after sitting under high vacuum for
6 h. R : 0.35 (50% CH Cl /hexanes on silica). The product
8
0045-4.; (c) Bloomer, J. L.; Zheng, W. Synth. Commun.
1
998, 28, 2087 doi:10.1080/00397919808007185.; (d) Bro-
mination in CHCl3: Mitchell, R. H.; Chen, Y.; Zhang, J.
Org. Prep. Proced. Int. 1997, 29, 715.
1
f
2
2
was purified via flash chromatography (50% CH Cl /hex-
2
1
2
(10) Orthobromination of phenols predominates in CS2: Carre n˜ o,
anes on silica). Yield: 95%, mp 25–26 8C. H NMR
M. C.; Urbano, A. Synlett 1997, 1241–1242.
(11) Goldberg, Y.; Alper, H. J. Org. Chem. 1993, 58, 3072.
doi:10.1021/jo00063a028.
(12) This study only investigated the bromination of pyrroles: Gi-
low, H. M.; Burton, D. E. J. Org. Chem. 1981, 46, 2221.
doi:10.1021/jo00324a005.
13) Mitchell, R. H.; Lai, Y.-H.; Williams, R. V. J. Org. Chem.
1979, 44, 4733. doi:10.1021/jo00393a066.
(14) Dijkstra, P. J.; den Hertog, H. J., Jr.; van Eerden, J.; Har-
kema, S.; Reinhoudt, D. N. J. Org. Chem. 1988, 53, 374.
doi:10.1021/jo00237a027.
15) Catalytic Koser’s reagent (HTIB) or TsOH was also added:
Bovonsombat, P.; McNelis, E. Synthesis 1993, 46, 237.
16) (a) Konishi, H.; Aritomi, K.; Okano, T.; Kiji, J. Bull. Chem.
Soc. Jpn. 1989, 62, 591 doi:10.1246/bcsj.62.591.; (b) Here,
the zeolite catalyst HZSM-5 (40:1 SiO2/Al2O3) was used in
CCl4: Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan, K. V.
Tetrahedron Lett. 1994, 35, 7055. doi:10.1016/0040-
(
6
300 MHz, CDCl ) d: 6.51 (s, 2H), 2.81 (s, 6H), 2.41 (s,
3
H). 13C NMR (100 MHz, CDCl ) d: 149.2, 138.2, 114.5,
3
+
1
1
12.7, 40.6, 24.1. GC-MS (8.12) [M] : 227.0. H NMR
52
spectrum is in agreement with that previously reported.
The compound was reported as a colorless liquid.
(
Bromojulolidine (referred to as 9-bromojulolidine in the
reference)
The product was extracted with CH Cl to produce a dark
2
2
53
red crystalline solid. Yield: 92%, mp 35–37 8C (lit mp
(
3
6.5 8C). R : 0.30 (CH Cl on silica). The product was puri-
f
2
2
1
fied via flash column chromatography (CH Cl on silica). H
2
2
(
NMR (300 MHz, CDCl ) d: 6.93 (d, J = 0.6 Hz, 2H), 3.17
3
(
t, J = 6.5 Hz, 4H), 2.76 (t, J = 5.7 Hz, 4H), 2.01 (m, 4H).
1
3
C NMR (100 MHz, CDCl ) d: 142.3, 129.6, 124.0, 107.5,
3
+
5
0.3, 28.0, 22.3, 28.0. GC-MS (10.85) [M] : 251.1.
4
039(94)88224-X.
4-Bromothioanisole
(
17) Here, silica gel was mixed with LiClO4: Bagheri, M.; Saidi,
Clear oil. GC conversion: 75%. R : 0.21 (hexanes on
M. R. Can. J. Chem. 2005, 83, 146. doi:10.1139/v05-001.
(18) Goldberg, Y.; Alper, H. J. Mol. Catal. 1994, 88, 377. doi:10.
1016/0304-5102(93)E0278-O.
(19) (a) Ganguly, N. C.; De, P.; Dutta, S. Synthesis 2005, 1103
doi:10.1055/s-2005-861866.; (b) Rajagopal, R.; Jarikote, D.
V.; Lahoti, R. J.; Daniel, T.; Srinivasan, K. V. Tetrahedron
Lett. 2003, 44, 1815. doi:10.1016/S0040-4039(03)00092-3.
20) Ca n˜ ibano, V.; Rodriguez, J. F.; Santos, M.; Sanz-Tejedor,
A.; Carre n˜ o, M. C.; Gonzales, G.; Garc ´ı a Ruano, J. L. Synth-
esis 2001, 2175. doi:10.1055/s-2001-18070.
f
1
silica). H NMR (300 MHz, CDCl ) d: 7.37 (d, J = 8.7 Hz,
3
2
[
H), 7.10 (d, J = 8.7 Hz, 2H), 2.46 (s, 3H). GC-MS (6.16)
+
M] : 201.9.
Acknowledgment
E.Z.-C. acknowledges le Fonds Qu e´ b e´ cois de la Re-
cherche sur la Nature et les Technologies (FQRNT) for
funding in the form of a post-doctoral scholarship.
(
(
21) Carre n˜ o, M. C.; Garc ´ı a Ruano, J. L.; Sanz, G.; Toledo, M.
A.; Urbano, A. J. Org. Chem. 1995, 60, 5328. doi:10.1021/
jo00121a064.
(22) Using similar conditions, the bromination of alkylnaptha-
lenes has also been investigated. See: Cammidge, A. N.; Fu-
gier, M. Synth. Commun. 1997, 27, 4159. doi:10.1080/
00397919708005463.
References
(
1) Garofalo, A. W.; Litvak, J.; Wang, L.; Dubenko, L. G.;
Cooper, R.; Bierer, D. E. J. Org. Chem. 1999, 64, 3369.
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(
2) Pulley, S. R.; Czako, B. Tetrahedron Lett. 2004, 45, 5511.
doi:10.1016/j.tetlet.2004.05.018.
(
(
3) Alvarez-Manzaneda, E. J.; Diaz, C. G. Synlett 2000, 1561.
4) Ross, S. D.; Finkelstein, M.; Petersen, R. C. J. Am. Chem.
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(23) The bromination of air sensitive julolidine (Table 1, entry
15) proceeded under a nitrogen atmosphere.
(24) For more polar products, such as 2-bromohydroquinone,
CH2Cl2 could be used to extract the product. Additionally,
unlike reactions in DMF,13 no oxidation to p-benzoquinone
was observed during the reaction.
(
5) Yadav, J. S.; Reddy, B. V. S.; Reddy, P. S. R.; Basak, A. K.;
Narsaiah, A. V. Adv. Synth. Catal. 2004, 346, 77. doi:10.
1
002/adsc.200303229.
6) (a) Lambert, F. L.; Ellis, W. D.; Parry, R. J. J. Org. Chem.
965, 30, 304; Here, catalytic HCl was used in acetone.
(
(25) Olah, G. A.; Arvanaghi, M.; Vankar, Y. D. Chem. Commun.
1979, 721.
1
doi:10.1021/jo01012a512.; (b) Andersh, B.; Murphy, D. L.;
(26) Chhattise, P. K.; Ramaswamy, A. V.; Waghmode, S. B. Tet-
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Published by NRC Research Press