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D. Suarez et al.
PAPER
2-(Bromomethyl)naphthalene (2h)
2-(Bromomethyl)-3,4-dichloro-1-nitrobenzene (2o)
Prepared from 2-methylnaphthalene; pale brown solid; yield: 85%;
2,3-Dichloro-6-nitrotoluene (5.0 g, 24.3 mmol) was stirred vigor-
ously in PhCF3 (50 mL) and H2O (50 mL) under N2 (no catalyst).
The mixture was illuminated with a 150 W tungsten bulb, and Br2
(16.0 g, 100 mmol, 5.1 mL) was slowly added. Workup was per-
formed as described in the general procedure above: pale yellow
solid; yield: 70%; Rf = 0.50 (PE–Et2O, 4:1).
mp 50–52 °C (Lit.12 51–53 °C); Rf = 0.34 (CH2Cl2–PE, 1:9).
1H NMR (300 MHz, CDCl3): d = 4.61 (s, 2 H, CH2Br), 7.43 (m, 3
H, Ar), 7.82 (m, 4 H, Ar).
2-(Bromomethyl)-6-methylpyridine (2i)
Prepared from 2,6-lutidine; pale brown solid; yield: 50%; mp 35–
37 °C; Rf = 0.42 (EtOAc–PE, 3:7).
1H NMR (300 MHz, CDCl3): d = 4.84 (s, 2 H, CH2), 7.55 (d, J = 8.9
Hz, 1 H, ArH), 7.79 (d, J = 8.9 Hz, 1 H, ArH).
1H NMR (300 MHz, CDCl3): d = 2.55 (s, 3 H, Me), 4.51 (s, 2 H,
CH2Br), 7.06 (d, 1 H, J = 9, Ar), 7.25 (d, 1 H, J = 6, Ar), 7.65 (m, 1
H, Ar).
Acknowledgment
This work was partly funded by the European Commission, contract
number HPRN-CT-2002-00195, ‘Cobalamins & Mimics’.
MS (EI, 70 eV): m/z (%) = 185 (<1) [M+], 122 (10), 106 (100), 79
(28).
2,6-Bis(bromomethyl)pyridine (2j)
References
Prepared from 2,6-lutidine; white solid; yield: 45%; mp 80–82 °C
(lit.13 83–86 °C); Rf = 0.48 (EtOAc–PE, 2:8).
(1) Encyclopedia of Reagents for Organic Synthesis, Vol. 1;
Paquette, L. A., Ed.; Wiley: Chichester, 1995, 768–772.
(2) Re-evaluation of Some Organic Chemicals, Hydrazine and
Hydrogen Peroxide, 1st ed., Part II, Vol. 71; IARC: Lyon,
1999, 401–432.
1H NMR (300 MHz, CDCl3): d = 4.47 (s, 4 H, CH2Br), 7.30 (d, 2 H,
J = 6 Hz, Ar), 7.64 (m, 1 H, Ar).
4-(Bromomethyl)-2,6-di-tert-butylpyridine (2k)
Prepared from 2,6-di-tert-butyl-4-methylpyridine; colorless oil at
r.t.; yield: 61%; Rf = 0.58 (hexane).
(3) Amijs, C. H. M.; van Klink, G. P. M.; van Koten, G. Green
Chem. 2003, 5, 470.
(4) Maul, J. J.; Ostrowski, P. J.; Ublacker, G. A.; Linclau, B.;
Curran, D. P. Top. Curr. Chem. 1999, 206, 79.
(5) Radleys Carousel from Radleys Discovery Technologies;
Shire Hill, Saffron Walden, Essex, CB11 3AZ, UK
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1996, Entry 1142.
(7) Offermann, W.; Vögtle, F. Angew. Chem., Int. Ed. Engl.
1980, 19, 464; Angew. Chem. 1980, 92, 471.
(8) Fernandez, R. PhD Thesis; University of Newcastle upon
Tyne: UK, 2002.
1H NMR (300 MHz, CDCl3): d = 1.27 (s, 18 H, Me), 4.30 (s, 2 H,
CH2Br), 7.01 (s, 2 H, Ar).
4-(Dibromomethyl)-2,6-di-tert-butylpyridine (2l)
Prepared from 2,6-di-tert-butyl-4-methylpyridine; white solid;
yield: 55%; mp 72–74 °C; Rf = 0.63 (hexane).
IR (KBr): 3045, 2895, 1524, 604 (C–Br) cm–1.
1H NMR (300 MHz, CDCl3): d = 1.29 (s, 18 H, Me), 6.46 (s, 1 H,
CHBr2), 7.18 (s, 2 H, Ar).
MS (EI, 70 eV): m/z (%) = 365 [M+], 363 (50%) [M+], 361 [M+],
350 (55), 348 (100), 346 (61).
(9) Sket, B.; Zupan, M. J. Org. Chem. 1986, 51, 929.
(10) Makhija, M. T.; Kasliwal, R. T.; Kulkarni, V. M.; Neamati,
N. Bioorg. Med. Chem. 2004, 12, 2317.
Anal. Calcd for C14H21NBr2: C, 46.31; H, 5.83; N, 3.86. Found: C,
46.35; H, 5.85; N, 3.91.
(11) Togo, H.; Hirai, T. Synlett 2003, 702.
(12) Waykole, L.; Prashad, M.; Palermo, S.; Repic, O.;
Blacklock, T. J. Synth. Commun. 1997, 27, 2159.
(13) Offermann, W.; Vögtle, F. Synthesis 1977, 272.
(14) Hou, C. J.; Okamoto, Y. J. Org. Chem. 1982, 47, 1977.
(15) Deshpande, A. M.; Natu, A. A.; Argade, N. P. J. Org. Chem.
1998, 63, 9557.
(16) Podgoršek, A.; Stavber, S.; Zupan, M.; Iskra, J. Tetrahedron
Lett. 2006, 47, 7245.
(17) Shaw, H.; Perlmutter, H. D.; Gu, C.; Arco, S. D.; Quibuyen,
T. O. J. Org. Chem. 1997, 62, 236.
3-(Bromomethyl)-4-methyl-2,5-furandione (2m)
Prepared from 3,4-dimethylfuran-2,5-dione; pale yellow oil; yield:
60%; Rf = 0.46 (Et2O–PE, 4:6).
1H NMR (300 MHz, CDCl3): d = 2.12 (s, 3 H, Me), 4.12 (s, 2 H,
CH2Br).
2-(Bromomethyl)-3-nitropyridine (2n)
Prepared from 2-methyl-3-nitropyridine;18 yellow oil; yield: 37%;
Rf = 0.27 (CH2Cl2–PE, 7:3).
(18) Cash, M. T.; Schreiner, P. R.; Phillips, R. S. Org. Biomol.
Chem. 2005, 3, 3701.
1H NMR (300 MHz, CDCl3): d = 4.90 (s, 2 H, CH2Br), 7.45 [m, 1
H, pyridine C(4)H], 8.32 [d, 1 H, pyridine C(5)H], 8.75 [d, 1 H, py-
ridine C(3)H].
Synthesis 2009, No. 11, 1807–1810 © Thieme Stuttgart · New York